Thin-film battery devices and apparatus for making the same

ABSTRACT

A method and system for fabricating solid-state energy-storage devices including fabrication films for devices without an anneal step. A film of an energy-storage device is fabricated by depositing a first material layer to a location on a substrate. Energy is supplied directly to the material forming the film. The energy can be in the form of energized ions of a second material. Supplying energy directly to the material and/or the film being deposited assists in controlling the growth and stoichiometry of the film. The method allows for the fabrication of ultrathin films such as electrolyte films and dielectric films.

CROSS-REFERENCES TO RELATED INVENTIONS

This is a divisional of and claims priority to U.S. patent applicationSer. No. 09/815,919, filed: Mar. 23, 2001 now U.S. Pat. No. 6,962,613,titled “LOW-TEMPERATURE FABRICATION OF THIN-FILM ENERGY-STORAGEDEVICES,” which claims benefit of the following three U.S. ProvisionalPatent Applications: Application Ser. No. 60/191,774, filed: Mar. 24,2000, titled “COMPREHENSIVE PATENT FOR THE FABRICATION OF A HIGH VOLUME,LOW COST ENERGY PRODUCTS SUCH AS SOLID STATE LITHIUM ION RECHARGEABLEBATTERY, SUPERCAPACITORS AND FUEL CELLS”; Application Ser. No.60/225,134, filed: Aug. 14, 2000, titled “APPARATUS AND METHOD FORRECHARGABLE BATTERIES AND FOR MAKING AND USING BATTERIES”; andApplication Ser. No. 60/238,673, filed: Oct. 6, 2000, titled “BATTERYHAVING ULTRATHIN ELECTROLYTE,” each of which is incorporated byreference.

This invention also is related to the following six patent applicationseach filed on Mar. 23, 2001:

-   U.S. Ser. No. 09/815,983, titled “THIN-FILM BATTERY HAVING    ULTRA-THIN ELECTROLYTE AND ASSOCIATED METHOD;”-   U.S. Ser. No. 09/815,621, now abandoned, titled “INTEGRATED    CAPACITOR-LIKE BATTERY AND ASSOCIATED METHOD;”-   U.S. Ser. No. 09/816,628, now U.S. Pat. No. 6,805,998, titled    “METHOD AND APPARATUS FOR INTEGRATED-BATTERY DEVICES;”-   U.S. Ser. No. 09/816,603 titled “CONTINUOUS PROCESSING OF THIN-FILM    BATTERIES AND LIKE DEVICES;”-   U.S. Ser. No. 09/816,602, titled “DEVICE ENCLOSURES AND DEVICES WITH    INTEGRATED BATTERY;” and-   U.S. Ser. No. 09/815,884, titled “BATTERY-OPERATED    WIRELESS-COMMUNICATION APPARATUS AND METHOD;” each of which is    incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to solid-state energy-storage devices.More particularly, this invention relates to methods and systems forfabricating solid-state energy-storage devices and the resulting devicessuch as batteries and supercapacitors. The present invention alsorelates to solid-state energy-conversion devices, such as photovoltaicsand fuel cells, and associated methods.

BACKGROUND OF THE INVENTION

Electronics have been incorporated into many portable devices such ascomputers, mobile phones, tracking systems, scanners, etc. One drawbackto portable devices is the need to include the power supply with thedevice. Portable devices typically use batteries as power supplies.Batteries must have sufficient capacity to power the device for at leastthe length of time the device is in use. Sufficient battery capacity canresult in a power supply that is quite heavy or large compared to therest of the device. Accordingly, smaller and lighter batteries (i.e.,power supplies) with sufficient energy storage are desired. Other energystorage devices, such as supercapacitors, and energy conversion devices,such as photovoltaics and fuel cells, are alternatives to batteries foruse as power supplies in portable electronics and non-portableelectrical applications.

Another drawback of conventional batteries is the fact that some arefabricated from potentially toxic materials that may leak and be subjectto governmental regulation. Accordingly, it is desired to provide anelectrical power source that is safe, solid-state and rechargeable overmany charge/discharge life cycles.

One type of an energy-storage device is a solid-state, thin-filmbattery. Examples of thin-film batteries are described in U.S. Pat. Nos.5,314,765; 5,338,625; 5,445,126; 5,445,906; 5,512,147; 5,561,004;5,567,210; 5,569,520; 5,597,660; 5,612,152; 5,654,084; and 5,705,293,each of which is herein incorporated by reference. U.S. Pat. No.5,338,625 describes a thin-film battery, especially a thin-filmmicrobattery, and a method for making same having application as abackup or first integrated power source for electronic devices. U.S.Pat. No. 5,445,906 describes a method and system for manufacturing athin-film battery structure formed with the method that utilizes aplurality of deposition stations at which thin battery component filmsare built up in sequence upon a web-like substrate as the substrate isautomatically moved through the stations.

FIG. 1A shows a prior art thin-film battery 20 formed on substrate 22.The battery includes a cathode current collector 32 and an anode currentcollector 34 formed on the substrate 22. A cathode layer 38 is formed onthe cathode current collector 32. An electrolyte layer 42 is formed onthe cathode layer 38. An anode layer 44 is formed on the electrolytelayer 42, the substrate 22 and the anode current collector 34. Thecurrent collectors 32 and 34 are connected to external circuitry toprovide electrical power to the same. In a discharge operation, ions inthe anode layer 44 travel through the electrolyte layer 42 and arestored in the cathode layer 38. Thereby, creating current flowing fromthe anode current collector 34 to the cathode current collector 32. In acharge operation, an external electrical charge is applied to thecurrent collectors 32 and 34. Thereby, ions in the cathode layer 38 areforced to travel through the electrolyte layer 42 and are stored in theanode layer 44.

FIG. 2A shows a prior art method for fabricating the thin-film battery20. First, the substrate is prepared for deposition of the thin-filmbattery (step 215). The cathode current collector is deposited on thesubstrate using DC-magnetron sputtering (step 217). The cathode isdeposited on the cathode current collector by RF-magnetron sputtering(step 219). In this method, the magnetron source provides sputteredmaterial having energy of about 1–3 eV, which is insufficient tocrystallize the cathode material to form desirable crystal structuresthat encourage ion movement into and out of the cathode material. Thecathode must be annealed to produce a crystalline lattice structure inthe cathode, which is necessary to produce an energy-storage device thathas the required electrical performance characteristics. In someembodiments, a desired electrical characteristic of a battery is adischarge curve that has a relatively constant voltage (small delta)over a range of capacity and then the voltage decreases rapidly asremaining capacity is exhausted (large delta). Accordingly, the stack ofthe substrate, cathode current collector and the cathode are annealed ata temperature of 700 degrees Celsius (step 221 of FIG. 2A). The annealstep 221 complicates and adds cost to the fabrication of this type ofsolid-state battery. Further, the anneal step 221 precludes the use ofany material as the substrate or other part of the battery thus formedthat is unable to withstand the high anneal temperature. The anodecurrent collector is deposited on the substrate by DC-magnetronsputtering (step 223). The electrolyte layer is deposited byRF-magnetron sputtering (step 225). The anode is deposited by thermalevaporation (step 227).

Accordingly, there is a need for solid-state energy-storage devices,e.g., thin-film batteries and capacitors, that can be rapidly fabricatedand that have acceptable electrical properties for use in a variety ofelectrical devices. More specifically, there is a need for a fabricationmethod and system that does not require a high-temperature anneal toform a solid-state energy-storage device.

SUMMARY OF THE INVENTION

A method and system is described for fabricating solid-stateenergy-storage devices. Some embodiments include fabricating films foran energy-storage device without an anneal step, especially without acathode anneal. The present invention provides energy focused at thelocation where it is needed to form a film having certain structuralcharacteristics. Accordingly, the total energy applied to the film andits support is less than if the energy was applied to the entire device,e.g., high temperature annealing the entire device. Thus, the presentinvention provides methods for applying energy to cure defects and/orcreate desired crystal structure at the time of depositing a film. Insome embodiments, the energy is applied essentially at a few atomiclayers at a time during deposition of a film.

In an embodiment as described herein, a film of an energy-storage deviceis fabricated by depositing a first material layer to a location on asubstrate. Energized ions of a second material are directed to the firstmaterial to supply energy thereto, thereby assisting the growth of thecrystalline structure of the first material. In some embodiments, thefirst material includes an intercalation material, which releasablystores ions therein. In one embodiment, the intercalation material is alithium intercalation material. In energy-storage devices, andspecifically in thin-film batteries, it is desirable to have largecrystal size and a specific crystal orientation to improve electricalcharacteristics of the energy-storage device.

Another aspect of the invention includes fabricating a layer of anenergy-storage device using a first source for supplying componentmaterial for the layer and a second source for supplying energy to alocation on the substrate at which the layer is to be deposited. In oneembodiment, the fabricated layer is the cathode for a thin-film battery.In another embodiment, the thin-film battery is a rechargeable,solid-state lithium-ion battery.

Another feature of the present invention is fabricating the electrolytefilm by depositing a first material layer to a location on a substrate.Energized ions of a second material are directed to supply energy to thefirst material, thus assisting the growth of the crystalline structureof the first material. Another feature of the present invention includesfabricating the anode film by depositing a first intercalation materiallayer to a location on a substrate. Energized ions of a second materialare directed to supply energy to the first material, thereby assistingthe growth of the crystalline structure of the first material andcontrolling stoichiometry of the crystalline structure of the firstmaterial.

Another aspect of the present invention includes controlling the energyprovided by the second source energized ions. The energized ions provideenergy to the intercalation material of about 5 eV or greater.

It is yet another aspect of the present invention to provide a seedlayer on which an intercalation film is grown. The seed layer assiststhe formation of desired crystal structures to improve energy-storagedevice performance.

Another feature of the present invention includes fabricating anenergy-storage device on any one of a plurality of different substrates.Some of the substrates have thermal degradation temperatures that areless than temperatures used for processes conventionally used for makingthin-film batteries. It is another feature to provide systems andfabrication techniques that do not cause temperature degradation of asubstrate or other layers thereon.

It is an aspect of the present invention to fabricate energy-storagedevices under economical manufacturing conditions.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a cross-sectional view of a conventional lithium-ion battery.

FIG. 1B is a cross-sectional view of an energy-storage device accordingto the present invention.

FIG. 1C is a cross-sectional view of an energy-storage device accordingto the present invention.

FIG. 1D is a cross-sectional view of an energy-storage device and asupercapacitor according to the present invention.

FIG. 2A is a flowchart of a conventional method for manufacturing thelithium-ion battery of FIG. 1A.

FIG. 2B is a flowchart of one embodiment of a fabrication processaccording to the teachings of the present invention.

FIG. 2C is a flowchart of one embodiment of a fabrication processaccording to the teachings of the present invention.

FIG. 2D is a flowchart of one embodiment of a fabrication processaccording to the teachings of the present invention.

FIG. 3A is a diagram of a device for fabricating a thin-film batteryaccording to the teachings of the present invention.

FIG. 3B is a diagram of a device for fabricating a thin-film batteryaccording to the teachings of the present invention.

FIG. 4 is a diagram of another embodiment of a device for fabricating athin-film battery according to the teachings of the present invention.

FIG. 5A is a diagram of another embodiment of a device for fabricating athin-film battery according to the teachings of the present invention.

FIG. 5B is a diagram of another embodiment of a device for fabricating athin-film battery according to the teachings of the present invention.

FIG. 6 is a diagram of another embodiment of a device for fabricating athin-film battery according to the teachings of the present invention.

FIG. 7 is a diagram of another embodiment of a device for fabricating athin-film battery according to the teachings of the present invention.

FIG. 8 is a cross-sectional view of a photovoltaic cell according to theteachings of the present invention.

FIG. 9A is a perspective view of a thin-film energy-storage deviceaccording to the teachings of the present invention.

FIG. 9B is a view of another embodiment of a thin-film energy-storagedevice according to the teachings of the present invention.

FIG. 9C is a view of another embodiment of a thin-film energy-storagedevice according to the teachings of the present invention

FIG. 10 shows X-ray diffraction spectra of cathode films for thin-filmbatteries.

FIG. 11 shows X-ray diffraction spectra of both a conventional cathodelayer and a cathode film according to the teachings of the presentinvention.

FIG. 12A shows X-ray diffraction spectra for a conventional magnetronsputtered cathode layer.

FIG. 12B shows X-ray diffraction spectra for a thin film for anenergy-storage device according to the present disclosure.

FIG. 13 is an exploded perspective view of an electronic device with aseparate printed circuit board and battery.

FIG. 14A is an exploded perspective view of a portion of an enclosurefor an electronic device according to one embodiment of this invention.

FIG. 14B is an exploded perspective view of a portion of an enclosurefor an electronic device according to another embodiment of thisinvention.

FIG. 14C is an exploded perspective view of a portion of an enclosurefor an electronic device according to yet another embodiment of thisinvention.

FIG. 15A is a plan view of a sheet including a plurality of batterycells.

FIG. 15B is a plan view of a diced battery cell before forming.

FIG. 15C is a perspective view of a battery cell after forming.

FIG. 15D is a perspective view of a battery cell after forming.

FIG. 15E is a perspective view of a battery cell after forming.

FIG. 15F is a plan view of a sheet including a plurality of batterycells.

FIG. 15G is a plan view of a plurality of diced battery cells beforeforming.

FIG. 15H is a perspective view of a fan folded plurality of dicedbattery cells before forming.

FIG. 15I is a plan view of a sheet including a plurality of batterycells.

FIG. 15J is a perspective view of a sheet including a plurality ofbattery cells formed on the sheet according to this invention.

FIG. 15K is a perspective view of a sheet including two battery cellsformed into a case from the sheet shown in FIG. 15J according to thisinvention.

FIG. 15L is a side view of an electronic device enclosure formed from asheet.

FIG. 16A is a plan view of a sheet including a plurality of batterycells.

FIG. 16B is a plan view of a diced battery cell before forming.

FIG. 16C is a perspective view of a fan folded diced battery cell beforeforming.

FIG. 16D shows a fan folded cord being truncated.

FIG. 16E shows a finished cord.

FIG. 17 is an exploded perspective view of a sheet including at leastone battery cell rolled around an electrical motor in accordance withthis invention.

FIG. 18A is a plan view of a diced battery cell and LED before forming.

FIG. 18B is a perspective view of a diced battery cell and LED afterforming.

FIG. 18C is a plan view of a diced battery cell and LED before forming.

FIG. 18D is a perspective view of a diced battery cell and LED afterforming.

FIG. 19A is a plan view of a sheet including a plurality of batterycells according to another embodiment of this invention.

FIG. 19B is a plan view of a plurality of diced battery cells beforeforming.

FIG. 19C is a perspective view of a formed battery including a pluralityof cells.

FIG. 20 is a cutaway side view of a sheet including a plurality ofbattery cells, which are embedded in an enclosure portion.

FIG. 21A is a flow chart for a first recycling method using theinventive battery and enclosure.

FIG. 21B is a flow chart for a first recycling method using theinventive battery and enclosure.

FIG. 22A shows a schematic circuit of an embodiment of an integratedbattery and circuit sharing a common terminal.

FIG. 22B shows a block diagram perspective view of an integrated deviceimplementing the circuit of FIG. 22A having the circuit built on thebattery.

FIG. 22C shows a block diagram perspective view of an integrated deviceimplementing the circuit of FIG. 22A having the battery built on thecircuit.

FIG. 22D shows a schematic circuit of an embodiment 2202 of anintegrated battery and circuit each having separate terminals.

FIG. 22E shows a block diagram perspective view of an integrated deviceimplementing the circuit of FIG. 22D having the circuit built on thebattery.

FIG. 22F shows a block diagram perspective view of an integrated deviceimplementing the circuit of FIG. 22D having the battery built on thecircuit.

FIG. 22G shows a block diagram perspective view of an integrated deviceimplementing the circuit of FIG. 22A having the battery and the circuitbuilt side-by-side on a substrate.

FIG. 22H shows a block diagram perspective view of an integrated deviceimplementing the circuit of FIG. 22D having the battery and the circuitbuilt side-by-side on a substrate.

FIG. 23 shows a perspective view of an embodiment 2300 of the presentinvention having a battery overlaid with circuitry.

FIG. 24A shows a perspective view of an embodiment 2400 of the presentinvention having a battery overlaid with an integrated device.

FIG. 24B shows a block diagram of a layer-deposition system 2460.

FIG. 24C shows a perspective view of a partially processed sheet 2464.

FIG. 24D shows a block diagram of a layer-deposition system 2465.

FIG. 24E shows a perspective view of a processed sheet 2469.

FIG. 24F shows a perspective view of a diced final device 2400.

FIG. 25A shows a perspective view of an embodiment 2500 of the presentinvention having an integrated circuit overlaid with a battery.

FIG. 25B shows a plan view of IC 2540.

FIG. 25C shows an elevational view of IC 2540.

FIG. 25D shows a plan view integrated battery-IC 2501.

FIG. 25E shows an elevational view of integrated battery-IC 2501.

FIG. 25F shows a block diagram of a layer-deposition system 2560.

FIG. 25G shows a perspective view of a processed sheet 2569.

FIG. 26A shows a perspective view of an embodiment 2600 of the presentinvention having an integrated circuit overlaid on its back with abattery.

FIG. 26B shows a block diagram of a layer-deposition system 2660.

FIG. 26C shows a perspective view of a processed sheet 2669.

FIG. 26D shows a perspective view of diced final devices 2600.

FIG. 26E shows a perspective view of wired diced final device 2600.

FIG. 26F shows a perspective view of a hearing aid 2690 incorporating awired diced final device 2600.

FIG. 27A shows a plan view of a starting substrate of an embodiment thatwill have an integrated battery and device sharing a common terminal.

FIG. 27B shows a plan view of the substrate of FIG. 27A after depositionof the integrated battery and device sharing a common terminal.

FIG. 27C shows a plan view of the substrate of FIG. 27B after placingand wiring a separately fabricated chip connected to the integratedbattery and device sharing a common terminal.

FIG. 27D shows a plan view of the substrate of FIG. 27C after placingand wiring a loop antenna.

FIG. 27E shows a plan view of the substrate of FIG. 27D after a topencapsulation layer has been deposited.

FIG. 27F shows an elevation view of the starting substrate of FIG. 27A.

FIG. 27G shows an elevation view of the partially built device of FIG.27B.

FIG. 27H shows an elevation view of the partially built device of FIG.27C.

FIG. 27I shows an elevation view of the partially built device of FIG.27D.

FIG. 27J shows an elevation view of the device of FIG. 27E.

FIG. 27K shows an perspective view of the device of FIG. 27E at amagnetic-recharging station.

FIG. 27L shows an perspective view of the device of FIG. 27E at alight-recharging station.

FIG. 27M shows a schematic of the device of FIG. 27E at aradio-wave-recharging station.

FIG. 28A shows an elevation view of a battery 2800 having stacked cells.

FIG. 28B shows a plan view of a single battery cell after recycling.

FIG. 28C shows a process 2810 used for recycling.

FIG. 29A shows a block diagram of a layer-deposition system 2960.

FIG. 29B shows a perspective view of a partially processed wafer 2964.

FIG. 29C shows a block diagram of a layer-deposition system 2965.

FIG. 29D shows a perspective view of a processed wafer 2969.

FIG. 29E shows a block diagram of a layer-deposition system 2965.

FIG. 29F shows a perspective view of a partially processed wafer 2974.

FIG. 29G shows a block diagram of a layer-deposition system 2960.

FIG. 29H shows a perspective view of a processed wafer 2979.

FIG. 29I shows a perspective view of wired diced final device 2600.

FIG. 30 is a perspective view of an implantable device according to thisinvention.

FIG. 31A is an exploded perspective view of a pacemaker according tothis invention.

FIG. 31B is an exploded perspective view of one pacemaker as it is beingformed.

FIG. 31C is an exploded perspective view of another pacemaker as it isbeing formed.

FIG. 32A is a perspective view of a first embodiment of a watch of theinvention.

FIG. 32B is a perspective view of a second embodiment of a watch.

In the drawings, like numerals describe substantially similar componentsthroughout the several views. Signals and connections may be referred toby the same reference number, and the meaning will be clear from thecontext of the description.

DETAILED DESCRIPTION

In the following detailed description of the preferred embodiments,reference is made to the accompanying drawings that form a part hereof,and in which are shown, by way of illustration, specific embodiments inwhich the invention may be practiced. It is to be understood that otherembodiments may be utilized and structural changes may be made withoutdeparting from the scope of the present invention.

It is to be understood that in different embodiments of the invention,each battery in the Figures or the description can be implemented usingone or more cells, and if a plurality of cells is implemented, the cellscan be wired in parallel or in series. Thus, where a battery or morethan one cell is shown or described, other embodiments use a singlecell, and where a single cell is shown or described, other embodimentsuse a battery or more than one cell. Further, the references to relativeterms such as top, bottom, upper, lower, etc. refer to an exampleorientation such as used in the Figures, and not necessarily anorientation used during fabrication or use.

The terms wafer and substrate as used herein include any structurehaving an exposed surface onto which a film or layer is deposited, forexample, to form an integrated circuit (IC) structure or anenergy-storage device. The term substrate is understood to includesemiconductor wafers, plastic film, metal foil, and other structures onwhich an energy-storage device may be fabricated according to theteachings of the present disclosure. The term substrate is also used torefer to structures during processing that include other layers thathave been fabricated thereupon. Both wafer and substrate include dopedand undoped semiconductors, epitaxial semiconductor layers supported bya base semiconductor or insulator, as well as other semiconductorstructures well known to one skilled in the art. Substrate is also usedherein as describing any starting material that is useable with thefabrication method as described herein.

The term battery used herein refers to one example of an energy-storagedevice. A battery may be formed of a single cell or a plurality of cellsconnected in series or in parallel. A cell is a galvanic unit thatconverts chemical energy, e.g., ionic energy, to electrical energy. Thecell typically includes two electrodes of dissimilar material isolatedfrom each other by an electrolyte through which ions can move.

The term adatom as used herein refers to a particle, molecule, or ion ofmaterial that has not yet been formed into a structure or film.

The term intercalation as used herein refers to a property of a materialthat allows ions to readily move in and out of the material without thematerial changing its phase. Accordingly, a solid-state intercalationfilm remains in a solid state during discharging and charging of anenergy-storage device.

FIG. 1B shows an embodiment of an energy-storage device 50 according tothe present invention. A substrate 55 is provided on which is formed acontact film 57. Contact film 57 acts as a current collector and isconnected to a lead 58, which connects one pole of the energy storagedevice 50 to an external circuit. An electrode film 59 is formed on thecontact film 57. In some embodiments, the electrode film 59substantially covers a surface of the contact film 57 to as to minimizeresistance by maximizing the area of the interface between the films. Insome embodiments, the electrode film 59 is a cathode for a thin-filmbattery. In other embodiments, electrode film 59 is an electrode of asupercapacitor. An electrolyte film 61 is formed on the electrode film59. An electrode film 63 is formed on the electrolyte film 61. Theelectrolyte film 61 isolates electrode film 59 from electrode film 63. Acontact film 65 is formed on electrode film 63. Contact film 65 acts asa current collector and is connected to a lead 67, which connects onepole of the energy storage device 50 to an external circuit. In someembodiments, the contact film 65 substantially covers a surface of theelectrode film 63 to as to minimize resistance by maximizing the area ofthe interface between these films. In some embodiments, the electrodefilm 63 is an anode for a thin-film battery. In other embodiments,electrode film 63 is an electrode of a supercapacitor.

FIG. 1C shows a cross sectional view of an embodiment of anenergy-storage device 50C. A substrate 55 is provided and, in someembodiments, includes additional layers and/or devices formed therewith.In some embodiments, the substrate 55 includes a substrate as describedherein. Contact films 57 and 59 are formed on the substrate 55 accordingto the methods described herein. In some embodiments, contact films 57and 59 are metal films deposited on the substrate according to othermethods as known in the art. Contact films 57 and 59 act as contacts forconnecting the energy-storage device 50C to other circuit elements (notshown).

An electrode first film 59 is formed on contact 57. Electrode first film59 includes a metal or intercalation material in some embodiments, forexample, thin-film battery embodiments in which the electrode first film59 functions as a cathode. In some such embodiments, the electrode firstfilm 59 includes lithium metal and/or a lithium-intercalation material.In other embodiments, such as supercapacitors, electrode first film 59is a metal oxide. It is desirable to maximize the contact interfacebetween the electrode first film 59 and contact film 57. Accordingly, insome embodiments, the electrode first film 59 substantially coverscontact film 57 except for a portion reserved for connection to externalcircuits.

An electrolyte film 61C is formed on, or at least partially on, theelectrode first film 59. The electrolyte film 61C, in some embodiments,completely encloses the electrode first film 59. The electrolyte film61C is formed using the systems and methods described herein. In oneembodiment, a first material of the electrolyte film 61C is depositedusing a first source, which directs a first electrolyte material(adatoms) to the location on the substrate or, as shown in FIG. 1C, to alocation on the electrode first film 59.

An electrode second film 59 is formed on electrolyte film 61C andcontact film 59. Electrolyte film 61C completely separates the electrodefirst film 59 from the electrode second film 59. The electrode secondfilm 63 includes a metal or intercalation material in some embodiments,for example, thin-film battery embodiments in which the electrode secondfilm is an anode. In other embodiments, such as supercapacitorembodiments, electrode second film 63 is a metal oxide. Electrode secondfilm 63, in some embodiments is deposited according to the methodsdescribed herein. In other embodiments, electrode second film 63 isformed according to methods known in the art.

The electrolyte film 61C as deposited includes the electrolyte material.A first source (e.g., sources 311, 511, 511A, and 711 as describedherein) of the electrolyte material, in one embodiment, is a physicalvapor deposition source. In another embodiment, the first source is achemical vapor deposition source. A second source provides energizedparticles to the location. The energized particles impinge on theelectrolyte material and assist in forming a desired structure of theelectrolyte film 61C. In some embodiments, the second source providesenergized particles simultaneously with the first source supplying theelectrolyte material. The use of the energized particles conforms theelectrolyte film 61C to electrode first film 59 such that theelectrolyte film provides the necessary insulative property, namelypreventing electrons from travelling directly between the electrodefirst film 59 and the electrode second film 63, i.e., shorting theelectrodes. In some embodiments, the second source is an ion source asdescribed herein, e.g., sources 313, 413, or 713. The second sourceprovides energized ions that supply energy to the electrolyte materialfrom the first source. The energy that is supplied by the ions assistsin conforming the formed electrolyte film 61C to the electrode firstlayer 59. It is believed that the use of the energized particles in theenergy range referenced herein provides the growing electrolyte materialan extended period of mobility upon the previous film surface, and thisextended period of mobility allows the electrolyte material to grow in amore defect-free manner.

In some embodiments, it is desired to form the electrolyte film 61C asthin as possible to lower its contribution to the internal resistance ofthe energy-storage device. It is also desired to maintain theelectrolyte's property of blocking the flow of electrons (which wouldresult in a short of the cathode to the anode) while permitting the flowof the ions that provide the battery function across the electrolyte.Using the methods and systems described herein, the electrolyte film 61Cis formed to a thickness 61C′ of less than about 5000 Angstroms. In someembodiments, the electrolyte film 61C has a thickness 61C′ of less thanabout 2500 Angstroms. In some embodiments, the electrolyte film 61C hasa thickness 61C′ of less than about 1000 Angstroms. In some embodiments,the electrolyte film 61C has a thickness 61C′ of less than about 500Angstroms. In some embodiments, the electrolyte film 61C has a thickness61C′ of less than about 250 Angstroms. In some embodiments, theelectrolyte film 61C has a thickness 61C′ of less than about 100Angstroms. In some embodiments, the electrolyte film 61C has a thickness61C′ in a range of about 10 Angstroms to about 200 Angstroms. In someembodiments, the electrolyte film 61C has a thickness 61C′ in a range ofabout 10 Angstroms to about 100 Angstroms.

In one embodiment, the electrolyte film 61C includes LiPON and is formedusing the first source 311 with the second source 313 or 413. As usedherein, LiPON refers generally to lithium phosphorus oxynitridematerials. One example is Li₃PO₄N. Other examples incorporate higherratios of nitrogen in order to increase lithium ion mobility across theelectrolyte. In some embodiments, the first source 311 provides Li₃PO₄in a nitrogen atmosphere. In other embodiments, the first source 311provides Li₃PO₄ in a vacuum environment wherein the background pressureis less than 1E−3 Torr. The second source 313 or 413 provides energizedparticles from a source gas. In some embodiments, the secondary sourceis an ion source supplying energetic ions from a source gas comprisingoxygen (e.g., O₂) or nitrogen (e.g., N₂). The source gas, in otherembodiments, comprises a noble gas, e.g., argon, xenon, helium, neon,and krypton. The energized particles and/or ions increase the energy ofthe material forming the electrolyte film 61C, thus enhancinglayer-by-layer growth. Accordingly, the electrolyte film is of a higherquality than conventional electrolyte layers.

An embodiment for forming a LiPON electrolyte film 61C includes thefirst source providing Li₃PO₄ at or to the location where the LiPONelectrolyte film is to be formed and second source providing energizednitrogen particles to or near the same location. The energized nitrogenparticles react with Li₃PO₄ provided at the location for forming theelectrolyte film. This increases the amount of nitrogen in the LiPONelectrolyte film. Increasing the nitrogen content is desirable toincrease lithium ion mobility across the electrolyte.

In a further embodiment, the chamber in which the substrate 55 ispositioned has a nitrogen enhanced atmosphere. A LiPON electrolyte film61C is formed by the Li₃PO₄ supplied by the first source reacting withthe nitrogen in the chamber. The second source provides energizedparticles assisting in the formation of the electrolyte film. In anotherembodiment, the second source also provides nitrogen to the Li₃PO₄ atthe location. Thus, the Li₃PO₄ reacts with both the nitrogen in thechamber and with energized, nitrogen containing particles supplied bythe second source. This increases the nitrogen content of theelectrolyte film 61C. In some embodiments, increasing the nitrogencontent in the electrolyte film 61C is desirable since published datafrom the Department of Energy lab at Oak Ridge, Tenn. indicates anincrease in nitrogen content increases the ion conductivity or mobilityin the electrolyte film.

As will be understood by reading the present invention, the systemsshown herein for depositing films are adaptable to form the electrolytefilm 61C according to the present invention. Examples of some suchsystems are shown in FIGS. 3–7.

FIG. 1D shows another embodiment of an energy storage device accordingto the teachings of the present invention. A supercapacitor 70 is formedon the energy-storage device 50C having the ultra-thin electrolyte film61. The energy-storage device 50C being formed on the substrate prior toforming the supercapacitor 70 represents an embodiment of layer/devicesbeing formed on the substrate prior to applying the techniques describedherein to form energy-storage and/or energy conversion devices. Thesupercapacitor 70 includes an intermediate film 73 formed in physicalcontact with electrode films 71 and 75. In some embodiments, theintermediate film 73 is an electrolyte for storing and dischargingelectrical charge by a faradaic process. In some embodiments, theintermediate film 73 includes a dielectric material. The contact film 65is in physical and electrical contact with electrode 71. Thus, in thisembodiment contact film 65 is a shared contact film for both the energystorage device 50C and supercapacitor 70. In other embodiments, energystorage device 50C and supercapacitor 70 have separate contact films. Insome embodiments, the intermediate film 73 includes LiPON. In someembodiments, the electrolyte film 73 includes TaO. In some embodiments,the electrode films are RuO₂. A contact film 77 is formed on theelectrode film 75. A lead 76 extends from the contact film 77 to contactone plate of the supercapacitor to an external circuit.

A method for fabricating the solid-state energy-storage device 50 willnow be described with reference to FIGS. 1B and 2B. The method includesproviding a substrate 55 (step 251) and depositing a cathode contactfilm 57 on the substrate 55 (step 253). In some embodiments, step 251includes providing a substrate having insulator layers or otherlayers/devices formed thereon. The method further includes a step 255 ofdepositing an electrode material to a location on the substrate, whilesimultaneously supplying energized particles to the electrode materialat the substrate. In one embodiment, an assist source provides theenergized particles. In some such embodiments, the energized particlebeam is directed to the same location on the substrate as the electrodematerial. In an embodiment, the energized particles are energized ions.The energized ions, in an embodiment, include a material that isdifferent than the electrode material. The energized particles or theion beam assist in controlling growth of the structure of the electrodematerial at the location. In some embodiments, step 255 is used to forma cathode film or layer 59 for a solid-state, thin-film battery. Thecathode film 59 is in electrical and physical contact with the cathodecontact. An electrolyte film 61 is deposited, step 257, on the cathodefilm 59. An anode film 63 is deposited, step 259, on the electrolytefilm. The electrolyte film 61 separates the cathode and anode films 59and 61 to prevent shorting the energy-storage device 50, e.g., battery.An anode contact is formed, step 261, in electrical and physical contactwith the anode film. The thin-film battery according to the presentinvention is now formed and is subjected to post energy-storage devicefabrication steps 263.

The deposition of the cathode film includes directing a first material(e.g., adatoms) to a location on the substrate, while simultaneouslysupplying energized particles (e.g., ions) of a second material to thelocation on the substrate. In some embodiments, the second material isdifferent from the first material. The energized particles supply energyto the first material to assist in the growth of a desirable crystalstructure in the cathode film. Moreover, this controls the stoichiometryof the growing film at the location on the substrate. In one embodiment,the first material is a lithium-intercalation material used as asolid-state, thin-film battery cathode. The assist source provides ionsthat provide energy in a range of 5 eV to 3000 eV to thelithium-intercalation material. Control of the energy in the ionsproduced by the assist source provides in situ control for growing alithium-intercalation film having a crystalline structure. The energyfrom the ions assists the formation of lithium-intercalation materialsinto a crystalline structure at the time of deposition. In oneembodiment, the gas used to form the ions is used to control thestoichiometry of the growing, crystalline film. For example, an ionized,assist beam of O₂ is used to control the growth and stoichiometry of aLiCoO₂ intercalation material. In some such embodiments, the O₂ in theion assist beam combines with LiCo at the location to form the LiCoO₂intercalation material.

The crystalline structure of a thin film formed according to theteachings herein has a higher order than those achieved by conventionalcathode film forming techniques. Conventional techniques rely on ahigh-temperature, post-cathode-deposition anneal to reorder andcrystallize the structure of a conventional cathode film. Unfortunately,such conventional techniques anneal the entire structure to the sametemperatures, which is undesirable in that the substrate must withstandsuch temperatures which eliminates many otherwise suitable substratematerials from consideration. Further, different layers cannot beprovided with different anneals suited to their different requirements.A highly ordered crystalline cathode film is desirably achievedaccording to the teachings described herein by providing the requiredenergy to form the desired, high-order and appropriately orientedcrystal structure without subjecting the substrate, and other layersformed on the substrate including the cathode-contact film to ahigh-temperature anneal. Further, each layer can be annealed using adifferent anneal process (such as using ion assist beams havingdifferent energies for different layers, or depositing and annealing atdifferent rates or for different durations). Further, by annealing thesurface layer of the previous layer, a subsequent layer can be depositedonto a surface that has been ordered in a specific way (for example, toachieve a specific crystal orientation, or a specific ion-bondingsurface) that enhances the quality of that subsequent layer.

FIG. 2C shows one embodiment of a method for fabricating anenergy-storage device. Steps 251, 253, 259, 261, and 263 aresubstantially similar to the steps described above with reference toFIG. 2B. Step 255C is a step for depositing a cathode film at leastpartially on the cathode contact film. In an embodiment, the cathodefilm is deposited as described above in step 255. In other embodiments,the cathode film-is deposited according to other deposition processesknown in the art. The electrolyte film is formed by depositing anelectrolyte material to a location at least partially in contact withthe cathode film (step 257C). In a preferred embodiment, the electrolytematerial is in contact with a substantial portion of, if not all of, asurface of the cathode film. In some embodiments, an assist sourcesimultaneously supplies energized particles to the electrolyte materialas it forms the electrolyte film. In an embodiment, the assist sourcesupplies a beam of energized ions of an assist material different thanthe electrolyte material. In one embodiment, the second material beam isdirected to the same location on the substrate as the electrolytematerial. The energized ion beam assists in controlling growth of thestructure of the electrolyte film. The ion beam is unfocused in oneembodiment. The ion beam is focused in another embodiment.

The deposition of the electrolyte film includes directing an electrolytematerial to a location at least partially in contact with the cathodefilm, while simultaneously supplying energy to the electrolyte material.In one embodiment, the energy is supplied by energized particles. Insome such embodiments, the energized particles are energized ions. Insome such embodiments, the energized particles from the assist sourceare of a different material than the electrolyte material. The energizedparticles supply energy to the electrolyte first material to assist inthe growth of a desirable, solid electrolyte-film structure. Moreover,this controls the stoichiometry of the growing electrolyte film.

In one example, the electrolyte material is a lithium phosphorusoxynitride. In some embodiments, the assist source provides ions thatprovide energy in a range of about 5 eV to about. 5000 eV to the lithiumphosphorus oxynitride (“LiPON”). Control of the energy in the ionsproduced by the assist source provides in situ control for growing alithium phosphorus oxynitride structure at the location. The energy fromthe ions assists the formation of the lithium phosphorus oxynitridematerial into a desirable structure at the time of deposition. In oneembodiment, the gas used to form the ions is used to control thestoichiometry of the growing electrolyte film. For example, an ionizedassist beam of O₂ is used to control the growth and stoichiometry of alithium phosphorus oxynitride material. In another embodiment, anionized assist beam of N₂ is used. In this embodiment, the N₂ not onlycontrols growth and stoichiometry of the electrolyte film, but alsoinjects additional nitrogen into the electrolyte film. This is desirabledue to the ionic transportivity of a LiPON electrolyte film is dependanton the amount of nitrogen in the film.

FIG. 2D shows one embodiment of a method for fabricating anenergy-storage device. Steps 251, 253, 257, 261, and 263 aresubstantially similar to the steps described above with reference toFIG. 2B. Step 255C is a step for depositing a cathode film at leastpartially on the cathode contact film. In an embodiment, the cathodefilm is deposited as described above with reference to FIG. 2B. In otherembodiments, the cathode film is deposited according to other depositionprocesses known in the art. Step 259D is a step for depositing anelectrode material to a location at least partially on the electrolytefilm, while simultaneously supplying energized particles to theelectrode material. In one embodiment, the energized particles aredirected to the same location as the electrode material. In anembodiment, the energized particles are energized ions. The energizedions, in an embodiment, include a second material that is different thanthe first material. The energized particles or the ion beam assist incontrolling growth of the structure of the electrode material. Step259D, in some embodiments, is used to form an anode film for asolid-state thin-film battery. The anode film is in electrical andphysical contact with the anode contact and electrolyte films.

The deposition of the anode film includes directing an electrodematerial to a location at least partially in contact with theelectrolyte film, while simultaneously supplying energized particles ofa second material. The energized particles supply energy to theelectrode material to assist in the growth of a desirable crystalstructure in the anode film. Moreover, this controls the stoichiometryof the growing film. In one embodiment, the electrode material includesa lithium-intercalation material used as a battery anode. In anembodiment, the anode includes is a lithium metal or a lithium alloy. Inanother embodiment, the anode includes a carbonaceous material, such asgraphite or diamond-like carbon. In another embodiment, the anodeincludes a metal oxide, for example, RuO or VaO. In another embodiment,the anode includes a nitride material. A secondary source providesparticles, which are ions in some embodiments, that provide energy in arange of about 5 eV to about 3000 eV to the lithium-intercalationmaterial. Control of the energy in the ions produced by the secondarysource provides in situ control for growing a lithium-intercalationcrystalline structure at the location. The energy from the ions assiststhe formation of lithium-intercalation materials into a crystallinestructure at the time of deposition. In one embodiment, the gas used toform the ions is used to control the stoichiometry of the growing,crystalline film.

The crystalline structure of an electrode thin film formed according tothe teachings herein has a higher order than those achieved byconventional film forming techniques. Conventional techniques rely on ahigh-temperature, post-deposition anneal that affects the substrate andother layers as well as the film intended to reorder and crystallize thestructure of that film. In contrast, the present invention provides acontrolled energy source at the time of deposition or after the time ofdeposition that reorders the surface of the deposition film withoutsubstantially heating the underlying layers or substrate. In someembodiments, the energy is provided while depositing each atomic layerof a film such that each atomic layer is ordered as crystallizes intothe film. Examples of such energy sources include an ion beam thateither react with the adatoms being deposited and/or provide kineticenergy to assist in deposition of the film. Other examples of energysources include high temperature, short duration heat sources, shortduration plasma sources, lasers, other high intensity photo sources thatreorder the crystal structure adjacent the surface of the film withouteffecting other layers or the substrate. A highly ordered crystallinecathode or anode is desirably achieved according to the teachingsdescribed herein.

While the above fabrication process describes forming cathode and anodefilms in a certain order, other embodiments reverse the order of thecathode film and anode film. Moreover, the fabrication process describesforming cathode and anode films, for example in a battery. In someembodiments, the cathode and anode films are electrodes of a battery.Other embodiments include films forming various layers ofsupercapacitors. Supercapacitors operate In these embodiments, at leastone of the films forming the supercapacitor, e.g., electrode films 71,75 and electrolyte and/or dielectric film 73, have improved crystallinestructure, crystallite size, or fewer defects without resorting to ahigh temperature anneal of the entire structure to provide theseproperties. Accordingly, techniques and systems for fabricating thinfilms for use in an energy-storage device as described herein areapplicable to both solid-state batteries and solid-state capacitors.

In another embodiment, the thin-film energy-storage device is formed ona substrate. A contact film, which is electrically conductive and doesnot react with a subsequently deposited, adjacent cathode film, isformed on the substrate. The contact film acts as a barrier between thesubstrate and the cathode film. The contact film further acts as acurrent collector and as a connection between the cathode film andcircuits that are external to the energy-storage device. In anembodiment, the contact film has a thickness of greater than 0.3microns.

FIG. 3A shows a deposition apparatus 305 including a reaction chamber307 in which is positioned a substrate 309 on which an energy-storagedevice is to be fabricated. Reaction chamber 307, in one embodiment, isa sealed chamber that holds gases for the reaction and that provides asub-atmospheric pressure. In some embodiments, it is desirable to holdthe pressure in the chamber less than about 1×10⁻³ Torr. A firstmaterial source 311 is provided in the chamber 307. The first source 311produces a beam of adatoms 312 of a first material to be deposited onthe substrate 309. In one embodiment, the first material source 311 is aphysical vapor deposition source. In one such embodiment, the materialsource 311 is an e-beam source. In another such embodiment, the firstsource 311 is an arc source including, for example, a cathodic-arcsource, an anodic-arc source, and a CAVAD arc source. Arc sources areparticularly suited for use as a source as they effectively operate in achamber that is operated at low temperatures. In another embodiment, thefirst source 311 is a physical deposition source including, for example,a sputtering source. In another embodiment, the source 311 is a chemicalvapor deposition source including, for example, a direct ion sourceusing a hydrocarbon precursor gas. Beam 312 is focused on a location 319on the substrate 309 whereas the material of the beam 312 is depositedto form a film of an energy-storage device. An assist source 313 isprovided in the chamber 307 and produces a beam of energized particles314 directed at least adjacent to the location 319 on the substrate 309.In some embodiments, the assist source is an energized ion-producingsource. In some embodiment, the assist source 313 is offset from thefirst source 311 such that the beams from these sources are notcoincident. The energized particle beam 314 provides the energy that isrequired to control the growth and stoichiometry of the material in thefirst beam 312 into a crystalline structure on the substrate 309 as isexplained in greater detail herein. In one embodiment, the-energizedparticle beam 314 also provides elements that are required in the filmbeing deposited. In another embodiment, beam 314 is directed at leastnear location 319 such that sufficient energy to form the desiredcrystal structure and stoichiometry of the film being deposited issupplied by beam 314 to the material in first beam 312. In someembodiments, the deposition system 305 includes at least one additionalassist source 313A. In some embodiments, each of the sources 313Aprovides an additional assist beam 314A that provides energy to arrivingadatoms at the substrate. Various embodiments of assist beams 314 aredescribed below.

FIG. 3B shows another embodiment of a deposition apparatus 305. Theassist source 313 produces an energy beam 314 that travels along a paththat is essentially normal to the substrate 319. The source of materialto be deposited 311 is offset from assist source 313. In someembodiments, source 311 produces a beam of adatoms 312 that travelsalong a path that is non-normal to the substrate 319. The energy beamsupplies energy to the adatoms from beam 312 as described herein.

FIG. 4 is a view substantially similar to FIG. 3A, except thatdepositing apparatus 405 includes an assist source 413 for producing theenergized beam that is pivotally mounted to a bracket fixed in thechamber 307. The assist source 413 pivots to direct the energizedparticle beam 414 at a desired impingement angle to the surface of thesubstrate 309. In an embodiment, the impingement angle is in the rangeof about 15 degrees to about 70 degrees from normal to the substrate.Accordingly, in some embodiments, the impingement angle is variable. Inone embodiment, the impingement angle is about 45 degrees. In someembodiments, the deposition system 405 includes at least one additionalassist source 413A. In some embodiments, each of the sources 413Aprovides an additional assist beam 414A that provides energy to arrivingadatoms at the substrate. In some embodiments, the energy provided byassist beam 414 differs from the energy provided by at least one ofassist beams 414A. In some embodiments, the assist beam 414 and 414Aneed not simultaneously transmit energy to the adatoms. In someembodiments, the means by which the beams 414 and 414A transmit energyare different. In some embodiments, the material in beams 414 and 414Aare different.

FIG. 5A is a view substantially similar to FIG. 3 except that depositingapparatus 505 includes a plurality of first deposition sources 511. Inone embodiment, each one of the first deposition sources 511 directs itsrespective beam 512 to the location 319 on the substrate 309. In someembodiments, every one of the first sources 511 produces a beam 512including the same material. In other embodiments, at least of the firstsources 511 produces a beam 512 of a material that is different thanthat of another of the first sources 511. In some embodiments, thematerials from the plurality of first beams 512 combine at the location319 to form the desired film. In other embodiments, the materials infirst beams 512 combine with material from assist beam 314 to form thedesired film. In one embodiment, one of the first sources 511 directsits beam 512 to the substrate 319 but away from the location 319. Insome embodiments, a plurality of assist sources 313 provide energy tothe adatoms of beams 512.

FIG. 5B shows another embodiment of a depositing apparatus 505B. Aplurality of assist sources 313 is positioned to provide energy to aforming film at the substrate 319. A plurality of material sources 511A,511B, and 511C supply material to the chamber 307 and adjacent thesurface of the substrate 319. In some embodiments, each of the materialsources 511A, 511B, and 511C provide a same material and, thus, have theability to provide a greater quantity than one of the sources alone. Insome embodiments, at least one of the material sources 511A, 511B, and511C provides a material different than another of the material sources.In some embodiments, these different materials react at the in chamber307 to create the adatom material that will form a film on the substrate319. In some embodiments, at least one of the material sources 511A,511B, and 511C provides a precursor material into chamber 307 andanother of the material sources provides a reactant material into thechamber. The precursor and reactant material react together to createthe material that will form the film. In some embodiments, at least oneof the material sources 511A, 511B, and 511C includes a chemical reactorin which chemicals react. This source then injects the resultantmaterial into the chamber. The resultant material is included in thefilm fabrication process.

FIG. 6 is a view substantially similar to FIG. 5A except that depositingapparatus 605 includes a plurality of first deposition sources 511 and apivotable assist source 413. In some embodiments, this provides morematerial to a given deposition location. In some embodiments, thisprovides deposition at multiple locations. In still other embodiments,this allows different materials from different sources to be combined.

FIG. 7 shows another embodiment of a depositing apparatus 705 accordingto the teachings of the present invention. Depositing apparatus 705includes a reaction chamber 707 in which is positioned an elongate,flexible substrate 709 on which an energy-storage device is to befabricated. The substrate 709 is fed from a source roll 710 over anarched thermal control surface 715 and taken up by an end roll 718. Afirst material source 711 is provided in the chamber 707 and is aphysical deposition source. First source 711 produces a beam of adatoms712 of a material to be deposited on the substrate 709. In oneembodiment, the first source 711 is an arc source including, forexample, a cathodic arc source, an anodic arc source, and a CAVAD arcsource. In another embodiment, the first source 711 is a physical vapordeposition source including, for example, a sputtering source. Inanother embodiment, source 711 is a chemical vapor deposition source.Moreover, source 711, in some embodiments, represents a plurality ofdifferent material sources. Beam 712 is focused on a location 719 on thesubstrate 709 whereas the adatoms in the beam are deposited to form afilm layer of an energy-storage device. An assist source 713 is providedin the chamber 707 and produces a beam of energized particles 714directed at the substrate 709. In an embodiment, the assist source 713produces a beam of energized ions 714. The energized particle beam 714provides the energy required to control growth and stoichiometry of thedeposited material of the first beam 712. Thus, a crystalline structureis formed on the substrate 709 as is explained in greater detail herein.The substrate 709, in one embodiment, is an elastomer, polymer, orplastic web or sheet on which the energy-storage device is fabricated.Substrate 709, being elongate, allows a plurality of energy-storagedevices to be deposited on successive locations of the substrate,thereby improving the rate of energy device production. Moreover, aplurality of deposition apparatuses 705 or sources 711, in someembodiments, are provided for simultaneously depositing a plurality offilms at different locations on the substrate 709.

The thermal control surface 715 is connected to a thermal source 725,which controls the temperature of surface 715. The substrate 709 is inthermodynamic contact with surface 715 to thereby control thetemperature of the substrate as needed for a particular depositionprocess on a particular substrate. In one embodiment, the thermal sourceis a coolant source, for example a cryogenic vacuum pump that releasescompressed helium toward the surface 715 to cool it. The use of athermally controlled surface 715 in direct contact with the substrate709, especially when the direct contact is aligned or coincident withthe location whereas a thin film is being formed, allows the use ofsubstrates that have lower thermal degradation temperatures than arepossible using conventional solid-state thin-film battery fabricationprocesses.

The above provides descriptions of various embodiments of systems inwhich the present invention is performed to produce energy-storagedevices or energy-conversion devices. It is within the scope of thepresent invention to combine the elements of the systems in differentways than shown and described as long as the methods described hereinare performable with such a system. For example, in some embodiments,the flexible substrate 709 and rolls 710, 718 can be combined with anyof the embodiments shown in FIGS. 3A–6. In some embodiments, the thermalsource 725 is also combinable with any of the embodiments of FIGS. 3A–6.In some embodiments, the pivotable assist sources 413 are combinablewith any of the embodiments of FIGS. 3A, 3B, 5A, 5B, and 7. In someembodiments, the material sources 511A, 511B, and 511C are combinablewith embodiments of FIGS. 3A–5A and 6–7.

In one embodiment, the electrode second film, e.g., films 59 or 71 is alithium-intercalation material which overlays at least part of the firstfilm, e.g., contact films 57 or 63, but does not extend beyond theboundary of the first film. Thus, the intercalation second film remainsin a solid state during discharging and charging of the energy-storagedevice. In some embodiments, the second film is deposited using thefirst deposition source simultaneously with the secondary sourcesupplying energetic ions to the growing second film. In someembodiments, the first deposition source is a physical vapor depositionsource. In some embodiments, the secondary source is an ion sourcesupplying energetic ions from a source gas comprising oxygen (e.g., O₂)or nitrogen (e.g., N₂). The source gas, in another embodiment, comprisesa noble gas, e.g., argon, xenon, helium, neon, and krypton. The sourcegas, in yet another embodiment, comprises a hydrocarbon material such asa hydrocarbon precursor. Selection of the secondary source gas is basedon the desired effect on the stoichiometry of the deposited film. Thesecondary source, in one embodiment, provides a focused beam ofenergized ions. The secondary source, in one embodiment, provides anunfocused beam of energized ions. The energized ions provide energy tothe lithium-intercalation material in the range of about 5 eV to about3,000 eV. In one embodiment, the energy range of is about 5 eV to about1,000 eV. The energy range in a further embodiment is about 10 eV toabout 500 eV. The energy range in a further embodiment is about 30 eV toabout 300 eV. In another embodiment, the energy range is in the range ofabout 60 eV to 150 eV. In another embodiment, the energy range is about140 eV. In an embodiment, the second film has a thickness of greaterthan 10 microns. In one embodiment, the second film has a thickness inthe range of about 10 to 20 microns. In one embodiment, the second filmhas a thickness in the range of about 1 to 5 microns.

An electrolyte third film, e.g., films 61, 61C or 73, having ionictransport qualities but not being electrically conductive (anelectrolyte) is deposited so as to completely overlay the seconddeposited film. In one embodiment, the third film is deposited using afirst deposition source and a secondary source supplying energetic ionsto the growing film. In some embodiments, the first deposition source isa physical vapor deposition source. In some embodiments, the secondarysource is an ion source with the capability of supplying energetic ionshaving an energy greater than 5 eV. In another embodiment, the energyrange is about 5 eV to about 3,000 eV. In one embodiment, the energyrange of is about 5 eV to about 1,000 eV. The energy range in a furtherembodiment is about 10 eV to about 500 eV. The energy range in a furtherembodiment is about 30 eV to about 300 eV. In another embodiment, theenergy range is in the range of about 60 eV to 150 eV. In anotherembodiment, the energy of the ions from the secondary source is about140 eV. In some embodiments, the secondary source includes oxygen (e.g.,O₂) or nitrogen (e.g., N₂) gas. The secondary source gas, in anotherembodiment, includes a noble gas, e.g., argon, xenon, helium, neon, andkrypton. The secondary source gas, in another embodiment, includes ahydrocarbon material such as a hydrocarbon precursor. Selection of thesecondary source gas is based on the desired effect on the stoichiometryof the deposited film. The secondary source, in one embodiment, providesa focused beam of energized ions. The secondary source, in oneembodiment, provides a non-focused beam of energized ions. It isdesirable to make the electrolyte, third layer as thin as possible andprevent the cathode and anode layers from shorting. In an embodiment,the third film has a thickness of less than 1 micron. In one embodiment,the third film has a thickness in of less than 5,000 Angstroms. Inanother embodiment, the third film has a thickness of less than 1,000Angstroms. In another embodiment, the third film has a range of about 10Angstroms to about 100 Angstroms.

In another embodiment, the third film is deposited using a first sourcesupplying energetic ions (5 to 3000 eV) to a material source (target) atan impingement angle of 15 to 70 degrees and a second source supplyingenergetic ions to the growing film. The first deposition source includesa beam of focused energetic ions from a source gas. The source gasincludes one of the sources gases described herein.

An anode, fourth film, e.g., film 65 or 75 includes from alithium-intercalation material that is deposited on and overlays thethird film but not contacting first film (barrier) or second film(cathode). In one embodiment, the fourth film is deposited using a firstdeposition source simultaneously with a secondary source supplyingenergetic ions to the growing fourth film. In some embodiments, firstdeposition source is a physical vapor deposition source. In someembodiments, the secondary source is an ion source supplying energeticions from a source gas that includes oxygen (e.g., O₂) or nitrogen(e.g., N₂). The source gas, in another embodiment, includes a noble gas,e.g., argon, xenon, helium, neon, and krypton. The source gas, inanother embodiment, includes a hydrocarbon material such as ahydrocarbon precursor. Selection of the secondary source gas is based onthe desired effect on the stoichiometry of the deposited film. Thesecondary source, in one embodiment, provides a focused beam ofenergized ions. The secondary source, in another embodiment, provides anunfocused beam of energized ions. The energized ions provide energy tothe lithium-intercalation material in the range of about 5 eV to about3,000 eV. In one embodiment, the energy range of is about 5 eV to about1,000 eV. The energy range in a further embodiment is about 10 eV toabout 500 eV. The energy range in a further embodiment is about 30 eV toabout 00 eV. In another embodiment, the energy range is in the range ofabout 60 eV to 150 eV. In another embodiment, the energy range of theions from the secondary source is about 140 eV. In an embodiment, thefourth film has a thickness of greater than 10 microns. In oneembodiment, the fourth film has a thickness in the range of about 10 to40 microns.

In another embodiment, the fourth film is deposited by plasmadecomposition of hydrocarbon pre-cursor(s) at the surface of thesubstrate thereby forming a lithium-intercalation anode. In someembodiments, deposition is performed by plasma enhanced CVD usinghydrocarbon precursors. In one embodiment, the deposition includesdopants such as N₂. In one embodiment, a secondary source providesenergized ions to assist in the deposition of the fourth film. Theenergized ions provide energy in the range as described herein. In someembodiments, the secondary source is the same as any described herein.

In another embodiment, the anode, fourth film is deposited by direct ionbeam deposition of a lithium-intercalation material using hydrocarbonprecursors. The first deposition source provides a beam of focusedenergetic ions (5 to 3000 eV) from a source gas hydrocarbon precursordirected at the target material. In one embodiment, a secondary sourcesupplies energetic ions to assist in growing the fourth film and is asecondary source as described herein.

A contact, fifth film, e.g., film 65 or 77, which is electricallyconductive and does not react with the fourth film is formed in contactwith at least part of the fourth film. The fifth film does not contactthe second film (cathode). In an embodiment, the fifth film has athickness of greater than 0.5 microns. The fifth film acts as an anodecurrent collector for contact to external circuitry.

In some embodiments, a passivation, sixth film 79, which is electricallynon-conductive and chemically inert, essentially overlays theenergy-storage device as formed thus far, i.e., all the second, third,and fourth films, so that same are packaged and free from environmentalcontaminants that may react with these films and degrade performance ofthe energy-storage device. Environmental contaminants may includefurther fabrication materials for devices with the energy-storage deviceintegrated therewith. In some embodiments, the first and fifth contactfilms are partially exposed outside the sixth film for connection tocircuitry outside the energy-storage device.

The substrate 55, 309 or 709, on which the films described herein aredeposited, includes any material capable of supporting a thin film andbeing able to withstand the deposition process described herein. In oneembodiment, the substrate is formed of a material having a temperatureat which it will begin to degrade due to thermal effects of less than700 degrees Celsius. A further embodiment includes a substrate havingsuch a temperature at which it experiences thermal degradation of lessthan or equal to about 300 degrees Celsius. Thermal degradation of thesubstrate includes loss of shape of the substrate, loss of sufficientrigidity to support an energy-storage device, chemical breakdown of thesubstrate, cross-linking of materials on the substrate and/or films,melting, and combustion. Examples of substrates include silicon wafersand silicon on insulator structures. Other examples of substratematerials include metals on which an insulator layer is formed prior toformation of the energy-storage device as described herein. In anotherexample, the metal may act as a contact for the energy-storage devicewith insulator layers electrically separating the electrolyte film, theanode film and the anode contact from the metal substrate. Examples ofother materials that have a low thermal degradation temperature that aresuitable for fabricating an energy-storage device as disclosed hereininclude paper, fabrics (natural and synthetic), polymers, plastics,glasses, and ceramics.

The substrate 55, 309, or 709 has a form that is applicable to the typeof apparatus used to fabricate the energy-storage device according tothe teachings herein. One example of the substrate shape is asemiconductor wafer. Other forms of the substrate include elongate webs,weaves, foils, and sheets. It is within the scope of the presentinvention to provide a substrate having sufficient size on which aplurality of energy-storage devices and/or a plurality of energyconversion devices are fabricated.

One embodiment of the substrate 55, 309, or 709 includes a substratethat retains its support characteristics during an in situ temperaturetreatment. In the in situ temperature treatment, the substrate is placedin intimate contact with a thermally controlled surface, e.g., surface715. In one embodiment, the thermally controlled surface is a cooledsurface such that heat associated with deposition of any of the filmsdescribed herein are thermally balanced so as not to thermally degradethe substrate or any other structural element previously formed on thesubstrate. Thus, in some embodiments, substrates having low thermaldegradation temperatures, such as low melting points or low combustiontemperatures, are used as substrates in the present fabrication methods.For example, substrates include ceramics, glasses, polymers, plasticsand paper based materials. In an embodiment according to the teachingsherein, the substrate is a plastic or metal substrate on which aplurality of energy-storage devices is deposited. The substrate is thendivided into separate dies having at least one energy-storage devicethereon. The dies then can be worked, e.g., cold worked, into a desiredshape as dictated by the energy-storage device application.

In another embodiment, the substrate is made of a flexible material,e.g., substrate 709. The flexible substrate is formed into an elongateroll that is caused to pass over a curved object, which forces thematerial into intimate contact with the surface of the curved object.The curved object is a thermally controlled device (e.g., device 725 asshown in FIG. 7) to control the temperature of the substrate and balancethe effect of heat generated on the substrate and films thereon duringdeposition. For example, the object is hollow and sealed from theenvironment of the deposition vessel. In some embodiments, the hollowspace is filled with a coolant, e.g., cryogenic gas such as gas obtainedfrom LN₂ or liquid helium, with the coolant being constantlyreplenished. An area of intimate contact between the substrate andobject is coincident and opposite the location of material impingementon the substrate from the deposition source. In another embodiment, thecoolant is chilled water that is constantly being replenished. Inanother embodiment, the curved object is thermally controlled by anelectro-thermal cooling apparatus. In another embodiment, the curvedobject is a drum, which is either stationary or rotatable about its axisin the direction of substrate movement.

In another embodiment, the substrate 55 or 309 is formed of a strip ofrigid material. The rigid substrate is made to pass over a cooled,thermally controlled surface. Examples of the cooled surface aredescribed herein. One such example is a cooled surface that is cooled bythe release of cryogenic fluid such as liquid N₂ or liquid helium intopassages within the body of object having the surface but sealed fromthe environment of the deposition chamber. Other coolant sources includechilled water, cryogenic gas, and electro-thermal devices.

FIG. 8 shows a photovoltaic cell 800, e.g., solar cell, that includes atransparent electrode 810. Transparent electrode 810 includes atransparent supporting film 820 and a transparent, electricallyconductive film 830 formed on film 820. Examples of supporting film 820include glass and transparent plastics. In some embodiments, conductivefilm 830 includes indium tin oxide or tin oxide. In use, light 890,enters solar cell 800 through the transparent electrode 810. In someuses of embodiments, light 890 is solar light. A first semiconductorfilm 840 is positioned in contact with the transparent electrode 810. Asecond semiconductor film 860 is positioned in contact with the firstsemiconductor film 840, thereby, forming a semiconductor junction 850.In some embodiments, second semiconductor film 860 includes a bulk,highly doped region 862 and a high quality region 863 adjacent the firstsemiconductor film 840. In this embodiment, the junction is formed bythe first semiconductor film 840 and region 863. An electrical contactfilm 870 contacts the second semiconductor film 860. First and secondconductive leads 880 respectively contact the transparent, electricallyconductive film 830 and the electrical contact film 870 to carry poweraway from the cell.

In some embodiments, the materials and compositions of photovoltaic cell800 are conventional CdS/CdTe materials such as is described in U.S.Pat. No. 4,207,119, which is incorporated by reference; with theadditional processing according to the present invention to anneal ortreat the surface (e.g., by ion-assist beam) of the films as they aredeposited. In other embodiments, the compositions used are as describedin the following publications, each of which is incorporated byreference: R. W. Birkmire et al, “Polycrystalline Thin Film Solar Cells:Present Status and Future Potential,” Annu. Rev. Mater. Sci.1997.27:625–653 (1997); T. L. Chu et al, “13.4% Efficient thin-filmCdS/CdTe Solar Cells,” J. Appl. Phys. 70 (12) (15th Dec. 1991); T.Yoshida, “Photovoltaic Properties of Screen-Printed CdTe/CdS Solar Cellson Indium-Tin-Oxide Coated Glass Substrates,” J. Electrochem. Soc., Vol.142, No. 9, (September 1995); T. Aramoto et al., “16% EfficientThin-Film CdS/CdTe Solar Cells,” Jpn. J. Appl. Phys. Vol. 36 pp6304–6305 (October 1997); R. B. King, ed. “Encyclopedia of InorganicChemistry” Vol. 3., pp 1556–1602, John Wiley & Sons Ltd., (1994).

The brief description of the operation of a heterojunction, photovoltaicsolar cell that follows is to illustrate how the methodology of thepresent invention is applied to the fabrication of heterojunction,photovoltaic solar cells. It is believed that the present inventionprovides means and methods for fabricating photovoltaic cells havingsuperior efficiency.

In a heterojunction photovoltaic cell, the semiconductor films areformed of different materials. For a rectifying junction, thesemiconductor films must also be of different type, that is p or n type.The junction between the two semiconductor films is both a pn junctionand a heterojunction. The first semiconductor film on which solar lightis incident has a band gap higher than that of the second semiconductorfilm. The band gap of a semiconductor is the energy separation betweenthe semiconductor valance band and the conduction band. The band gap ofthis first semiconductor film is chosen so that it corresponds to lightin the short wavelength region of the solar spectrum. Photons of lighthaving energy equal to or greater than the band gap of the firstsemiconductor film are strongly absorbed, but photons of light of energyless than the band gap of the first semiconductor pass through the firstsemiconductor and enter the second semiconductor film. Examples ofmaterials used for the first semiconductor film include CdS, ZnS, CdZnS,CdO, ZnO, CdZnO, or other wide band gap semiconductors like SiC, GaN,InGaN, and AlGaN. The second semiconductor film is chosen from materialsthat have band gaps that correspond well to the long wavelength onset ofsolar radiation. Materials such as CdTe, CuInSe₂, InP, GaAs, InGaAs,InGaP, and Si are examples of materials for the second semiconductorfilm.

A “built in” electric field exists at the junction between the twosemiconductor films due to the migration of majority carriers from onesemiconductor type into the other. That is, electrons from the n-typesemiconductor migrate into the p-type semiconductor leaving a netpositive charge on the n-semiconductor side of the junction. Theconverse happens to the p-type semiconductor. Holes from the p-typesemiconductor migrate into n-type semiconductor leaving a net negativecharge on the p-semiconductor side of the junction. Absorption of aphoton in one of the semiconductor films 840, 860 results in thecreation of an electron and a hole. When the photon is absorbed in thevicinity of the pn junction, the built in electric field separates thetwo carriers in opposite directions, electrons are driven to the n-typematerial and holes are driven to the p-type film. The separated chargesresult in a potential difference between the two semiconductor films840, 860. This potential difference is used to drive a current throughan external circuit thereby converting solar energy (photons) intoelectrical energy.

One embodiment of a heterojunction, photovoltaic solar cell is ann-type, polycrystalline CdS film as the first semiconductor film 840 anda p-type, polycrystalline CdTe film as the second semiconductor film860. CdS has a band gap of 2.43 eV that corresponds to 510 nm. CdTe hasa band gap of 1.44 eV that corresponds to 860 nm. Solar radiationshorter than 860 nm and longer than 510 nm is absorbed in the p-typeCdTe semiconductor film 860. Each absorbed photon creates an electronhole pair. If the minority carrier, the electron in p-type CdTe, has alifetime sufficiently long so that it can drift to the pn junction andbe swept across the junction to the n-type CdS film, the absorbed photoncontributes to solar cell photocurrent. Minority carrier lifetimes inp-type CdTe are long, which results in high quantum efficiencies (numberof electrons created per number of photons absorbed at a particularwavelength) of ˜90% between 860 nm and 510 nm. Most photons absorbed inthe CdTe film contribute to the solar cell photocurrent.

Solar light at wavelengths shorter than 510 nm is absorbed in the n-typeCdS film and creates an electron-hole pair. Minority carriers in n-typeCdS, holes, have short lifetimes. Most photogenerated holes recombinewith electrons in the n-type CdS film before they can be swept acrossthe junction to the p-type CdTe film. Recombined electron-hole pairs donot contribute to the solar cell photocurrent. Creation of electron-holepairs by absorption of solar radiation in the CdS film is detrimental tothe overall efficiency of the solar cell. High-efficiency solar cellsmake the CdS film as thin as possible, ˜50 nm, so that some fraction ofsolar radiation shorter than 510 nm can pass through the CdS film and beabsorbed in the CdTe film where the photo-generated electron-hole pairscan be efficiently collected. A problem with this procedure is that, insome embodiments, thinning the n-type CdS film increases the seriesresistance of the cell, which also decreases the efficiency.Additionally, the CdS film must have some reasonable thickness, ˜50 nm,to form a stable pn junction.

The deposition methods according to the present invention are used toenhance the performance of heterojunction solar cells by creating higherquality semiconductor films 840, 860. In some embodiments, semiconductorfilms 840, 860 have structures that provide sufficiently longminority-carrier lifetimes to allow the minority carriers to be sweptacross the junction and contribute to the solar cell photocurrent. Insome embodiments, higher quality films 840, 860 are produced byproviding energy focused at the surface where a film is being formed. Insome embodiments, the energy is supplied simultaneously with thematerial to be deposited on a substrate. In some embodiments, higherquality films are created by depositing the primary material, forexample, CdS in the film 840, using a physical vapor depositiontechnique while impinging energized particles from a second source onthe film surface during the deposition. In some embodiments, the secondsource includes an ion source. In some embodiments, the ion sourceprovides a beam of ions. In some embodiments, the beam of ions includesargon or xenon. In some embodiments, the beam of ions includes sulfurfor depositing sulfide materials. In some embodiments, the beam of ionsincludes oxygen for depositing oxide materials. The effect of supplyingfocused energy is to increase the extent of crystallinity of thematerial being deposited. Another effect of supplying focused energy isto decrease defects that provide sites for electron-hole recombination.A further enhancement of the solar cell efficiency is achieved by usingthe focused energy to control the quality of the physical interfacebetween the first semiconductor film 840 and the second semiconductorfilm 860.

In an embodiment, the first film 840 is fabricated by providing energyto the material being deposited so that the material has fewer defects.With fewer defects the minority carriers will have longer lifetimes infilm 840 as the will be fewer recombination sites. In some embodiments,first film 840 includes an n-type CdS material. In some embodiments, thefirst film 840 is formed in a range of about 40 nanometers to about 100nanometers. In some embodiments, the first film 840 has a thickness ofabout 50 nanometers.

In some embodiments, the second film 860 includes two regions 862, 863.Region 863 is a high-quality region formed according to the teachings ofthe present invention. In some embodiments, region 862 is grown in afaster manner using conventional methods. In other embodiments, film 862is merely a further growth of film 863 using the teachings of thepresent invention. High quality includes, among other things, fewerdefects, larger crystal size, or certain structures being formed.Specifically, energy is supplied to the material of region 863 as thematerial is formed on the first film 840. The energy is suppliedaccording to the teachings herein, for example, by an ion-assist beam.In some embodiments, the energy is supplied by energized particles. Insome embodiments, the energy is supplied by energized ions. In someembodiments, the energy is supplied by light or heat, e.g., a brieflaser sweep of the surface. Due to the application of energy while theregion 863 is being formed, a post-deposition high-temperature anneal isnot required.

In some embodiments, the high quality region 863 has fewer defects thanp-type regions of other photovoltaics. In some embodiments, region 863has a thickness of at least about 50 nanometers. In some embodiments,region 863 has a thickness in a range of about 50 nanometers to about100 nanometers.

In some embodiments, region 862 is larger than region 863. In someembodiments, region 862 has a thickness of greater than 500 nanometers.In some embodiments, region 862 has a thickness in a range of 1 micronto 5 microns. In some embodiments, region 862 has a thickness of greaterthan 3 microns. In addition, region 862 is a highly doped p-typematerial.

In some embodiments, a chamber in which the films 840, 860 are beingdeposited is held at a temperature of less than 650 degrees Celsius. Insome embodiments, the temperature of the chamber is less than about 300degrees Celsius. In some embodiments, the temperature is between about30 degrees Celsius and about 275 degrees Celsius. In some embodiments,the temperature is between about 100 degrees Celsius and about 200degrees Celsius. In an embodiment, the substrate, e.g., glass layer 820and conductor layer 830 for depositing film 840; glass layer 820,conductor layer 830, and film 840 for depositing region 863; and glasslayer 820, conductor layer 830, film 840, and region 863 for depositingregion 862, is not externally heated. Thus, the temperature of thesubstrate is generally equal to the temperature of the chamber plusminor heating effects of depositing the film. In contrast to priormethods for fabricating layers having sufficient quality such that thecell approaches about 10 percent efficiency, an embodiment of thepresent invention does not heat the substrate. Accordingly,manufacturing efficiencies are achieved while maintaining sufficientefficiency.

It is believed that some embodiments of the present invention will haveconversion efficiencies of greater than about 5 percent. It is believedthat some embodiments of the present invention will have conversionefficiencies of greater than about 6 percent. It is believed that someembodiments of the present invention will have conversion efficienciesof greater than about 7 percent. It is believed that some embodiments ofthe present invention will have conversion efficiencies of greater thanabout 8 percent. It is believed that some embodiments of the presentinvention will have conversion efficiencies of greater than about 9percent. It is believed that some embodiments of the present inventionwill have conversion efficiencies of greater than about 10 percent. Itis believed that some embodiments of the present invention will haveconversion efficiencies of greater than about 11 percent.

Other embodiments for fabricating energy conversion devices, such as aphotovoltaic cell 800, are fabricated according to many of theembodiments described herein with reference to energy storage devices.The thin films of the energy conversion devices are improved in asimilar manner as described herein for the thin films of energy storagedevices.

In contrast to some conventional methods for improving performance of aphotovoltaic cell, the present methods can produce photovoltaic cellshaving an enhanced conversion efficiency without heat treating duringdeposition, e.g., heating the substrate, or a post-deposition hightemperature anneal.

FIG. 9A shows a thin-film energy-storage device 910A according to theteachings of the present disclosure and an integrated circuit 940, hereshown as a “flip chip”. Energy-storage device 910A includes substrate920 on which is formed a patterned wiring layer 922. The wiring layer922 is an electrically conductive layer for connecting energy-storagedevice 920 to the integrated circuit 940. In some embodiments, layer 922is formed of a metal. In one embodiment, the wiring layer 922 ispatterned copper. In another embodiment, the wiring layer is formed ofnickel. In other embodiments, the wiring layer is formed of a noblemetal. Wiring layer 922 includes a cathode wiring pattern 922A and ananode wiring pattern 922B, which are separate from each other and formopposite polarity connectors 923A and 923B to external circuitry, suchas integrated circuit 940. Device 910A further includes a cathodecontact film 924 formed on at least a portion of cathode wiring pattern922A and an anode contact film 926 formed on at least a portion of theanode wiring pattern 922B. A cathode film 927 is formed on the cathodecontact film 924 according to the teachings herein. An electrolyte film928 is formed over the cathode film 926, cathode contact film 924 and aportion of the cathode-wiring pattern 922A. Electrolyte film 928separates the cathode films 922A, 924 and 927 from respective anodefilms 922B, 926 and 932. Anode film 932 is formed on the electrolytefilm and in contact with the anode contact film 926 according to theteachings herein. It will be appreciated that, in one embodiment,cathode contact film 924 and cathode wiring pattern 922A are formed as asingle layer. It will be further appreciated that, in one embodiment,anode contact film 926 and anode wiring pattern 922B are formed as asingle layer. A passivation layer 934 is formed over all of the filmsexcept portions 923A and 923B of the wiring patterns 922A and 923B,which portions are left exposed. Passivation layer 934 protects thefilms from contact to other layers, which may be formed on substrate920, and the environment, which may include elements that may react withand damage the films of the energy-storage device 910A.

In some embodiments, the cathode materials and other materials used inthe batteries above include materials discussed more in N. J. Dudney etal, “Nanocrystaline Li_(x)Mn_(1-y)O₄ Cathodes for Solid-State Thin-FilmRechargable Lithium Batteries,” Journal of the Electrochemical Society,146(7) 2455–2464 (1999) which is incorporated by reference.

The integrated circuit 940 includes a first ball contact 941 and asecond ball contact 942 both extending outside a package. The first ballcontact 941 aligns with the exposed portion 923A of the cathode wiringpattern 922A. The second ball contact 942 aligns with the exposedportion 923B of the anode wiring pattern 922B. Integrated circuit 940 ispositioned so that the ball contacts 941 and 942 physically andelectrically contact the wiring contacts 923A and 923B, respectively.Integrated circuit 940 is fixed in position relative to the device 910Asuch that device 910A provides electrical energy to circuit 940. In someembodiments, circuit 940 is provided with circuitry for rechargingenergy-storage device 910A. It will be recognized that the presentinvention is not limited to only integrated circuit 940 being connectedto wiring contacts 923A and 923B. Other circuits, including integratedcircuits fabricated on substrate 920 and circuits with leads connectedto wiring contacts 923A and 923B, are within the scope of the presentinvention.

FIG. 9B shows another embodiment of the thin-film energy-storage device910B, substantially similar elements to those described above aredesignated by the same reference numerals. After forming wiring patterns922A, 922B, an insulator layer 930 is formed on the substrate 920.Insulator layer separates the thin-film energy-storage device 910 fromother layers that may be included with substrate 920. Insulator layer930 includes vias 931 through which cathode contact film 924 and anodecontact film 926 extend downward to connect to cathode contact wiringpattern 922A and anode wiring pattern 922B, respectively.

In one example of an energy-storage device 910 according to the presentinvention, the cathode film 927 is a LiCoO₂ deposited using a firstsource of LiCoO with a secondary source of oxygen. The electrolyte film928 is LiPON deposited using a first source of LiPO (such as Li₃PO₄) andan assist of nitrogen: The anode film 932 is a metal, e.g., copper, andis deposited by a first source of copper and a secondary source of aninert material, e.g., xenon. In another embodiment, the anode filmincludes carbon. In yet another embodiment, the anode is formed of purelithium. In some embodiments, the anode is a lithium alloy. In someembodiments, the anode includes an oxide.

FIG. 9C shows a further embodiment of a thin-film energy-storage device910C. This device 910C includes a seed layer 950 formed on the cathodecontact 924. Seed layer 950 is formed on the cathode contact 924 priorto forming the cathode film 927, as described herein, on the seed layer950 and substrate 920. Seed layer 950 is formed using depositiontechniques as described herein, e.g., physical vapor deposition such asarc source deposition. Seed layer 950 is a very thin, electricallyconductive layer and has a small crystal size. The seed layer 950 alsohas a high sheet resistance and is non-reactive with the materials ofadjacent films. In an embodiment, seed layer 950 has a thickness that issubstantially thinner than the adjacent electrode film 927. The materialof the seed layer 950 is chosen such that the arriving adatoms of thesubsequent material (e.g., in some embodiments, the material from thefirst source 311, 511 or 711) would have sufficient mobility to allow aperiod of activity once the adatom contacts the seed layer surface. Thisimproves nucleation of the first few molecular layers of arrivingmaterial, minimizes strain associated with lattice mismatch and assiststhe arriving material to grow in a manner consistent with the desiredcrystal structure for cathode film 927.

In some embodiments, a seed layer 955 is formed on the electrolyte layer928 prior to forming anode film 932, as described herein, on the seedlayer 955. Seed layer 955 improves nucleation of the first few molecularlayers of arriving material, minimizes strain associated with latticemismatch and assists the arriving material to grow in a mannerconsistent with the desired crystal structure for anode film 932.

The ion transport properties of the materials used in the fabrication ofenergy-storage devices 910C, e.g., rechargeable batteries, greatlyinfluence the operation and quality of the device. For example, thetotal energy-storage capability of solid-state, lithium-ion batteries ofa given area is limited by a depletion region that forms at or near thecathode/electrolyte interface. The depletion of this region and theinability for additional lithium ions to be transported out of the bulkof the cathode film 927 results in limited capacity and, thus, morefrequent recharges. Additionally, the efficiency of the lithium iontransport through the electrolyte film 928 controls and dictates themaximum discharge rate that can be achieved for a given structure. Theseed layer 950 improves the crystalline structure of the materialssubsequently deposited, i.e., a cathode film 927 or an anode film. Thegrowth of the first few atomic layers of a material significantlyimpacts its overall structure even when the final film is very thickrelative to the initial few atomic layers. If the “seed” material ischosen such that the surface energy kinetics are conducive topseudo-epitaxial growth of the subsequent material, high quality cathodeand anode (electrode) films 927 and 932 are achieved. Examples ofmaterials for seed layer 950 include chromium, chromium nitride,tantalum, tantalum nitride, tungsten, tungsten nitride, ruthenium andruthenium nitride.

The thin-film energy-storage device fabricated according to the presentteachings stores electrical energy by introducing ions into a storagelayer and removing the ions from the storage layer to create anelectrical potential at the contacts. In one embodiment, lithium ionsare stored in an anode formed of a lithium-intercalation material withthe battery in a charged state. In some embodiments, the anode is formedof a metal or a carbonaceous material. The lithium ions travel from theanode through the electrolyte layer to a cathode, which is also formedof a lithium-intercalation material, to discharge electrical energy fromthe battery. In order to achieve sufficient energy density to operateexternal circuitry, the lithium-intercalation material cathode and anodemust intercalate (i.e., add) and de-intercalate (i.e., remove) of asubstantial mole fraction of lithium ions. It has been found that thechoice of intercalation material and fabrication techniques for thecathode determine many operating parameters of a solid-state, thin-filmbattery. The operating parameters include, but are not limited to,operating voltage range, capacity, specific power, and specific energy.One method of measuring the transport properties of ions in a battery isdiffusivity, which is measured by a diffusion coefficient. The diffusioncoefficient is a measure of how well a particular material allows ionsto diffuse into and out of the material.

FIG. 10 shows comparative data for LiCoO₂ cathode films in the form ofX-ray diffraction spectra. The LiCoO₂ cathode films were createdaccording to the teachings herein and according to a control processthat did not include a secondary source assist. A first source supplieda LiCoO₂ material using an electron-beam evaporation process. An assist,second source provided energy in the form of oxygen ions impinging atthe location on the substrate whereas it is desired to grow a thinelectrode (cathode) film from the LiCoO₂ first material. The beam ofoxygen ions from the second source is not co-incident with the LiCoO₂material from the first source. Four samples of LiCoO₂ thin films weregrown according to the data in Table 1.

TABLE I Deposition Parameters Film a Film b Film c Film d Electron beam500 500 500 500 power* (W) Total gas flow, 0 10.8 10.8 10.8 O₂ + Ar,(sccm) O₂ gas ratio, NA 0.48 0.48 0.48 O₂/(O₂ + Ar), (%) Chamberpressure (Torr) 9.2 × 10⁻⁷ 2.6 × 10⁻⁶ 3.7 × 10⁻⁶ 5.0 × 10⁻⁶ Ion sourcepower (W) 0 123 128 135 Ion source acceleration 0 41 64 135 voltage (V)

The electron beam voltage for each first source used in forming filmsa–d is 5 kV with an emission current of 100 mA.

FIG. 10 shows that the LiCoO₂ films deposited with lower energy oxygenions from the second source, samples “b” and “c”, enhanced the formationof the desirable crystallite structure of the grown film relative to thenon-assisted sample “a”. Specifically, a more distinct (003) orientationof the crystal structure is found in ion-assisted samples “b” and “c”than in non-assisted sample “a”. A strong (003) X-ray diffraction peakindicates one desired crystal orientation of the LiCoO₂ thin film. The(003) X-ray diffraction peak indicates that the film has lattice planesparallel to the substrate, e.g., layer on which the film was deposited.The (003) peak width, full width at half maximum (“FWHM”) decreases andthe X-ray peak increases in this series of samples as the energy of theoxygen ions impinging the deposited material increases. These examplesindicate an increasing crystallite grain size and a larger fraction ofordered grains for sample films “b” and “c” than are found in samplefilm “a”. The (003) orientation of samples “b” and “c” is preferableover an essentially non-ordered, non-crystallized structure of sample“a”.

FIG. 10 further shows a sample “d” that was deposited using the highestenergy secondary source of this example. Sample “d” was deposited usinga secondary source energy of 135 eV. X-ray diffraction of sample “d”shows it has the most distinct (101) orientation of all the samplesdescribed herein. The desired (101) orientation has lattice planes,which contain lithium ions in a LiCoO electrode material, nearlyperpendicular to the substrate. In this orientation, the lattice planesare essentially parallel to the direction of travel of the ions and inthe direction nearly perpendicular to the substrate. As this is thedirection lithium ions must travel in a lithium battery fabricatedaccording to the embodiments described herein, the preferential (101)orientation leads to superior charging and discharging characteristics.As lithium transport through the LiCoO₂ film in the (101) preferentialorientation does not rely on diffusion along grain boundaries, which cantrap lithium ions and prevent their utilization, the preferential (101)orientation also leads to greater capacity and cycle lifetime.Consequently, this preferred orientation of the LiCoO₂ thin film isproduced without additional anneal fabrication steps and the internalresistance is lower with lower capacity loss at high discharge rates.

FIG. 11 shows a comparison of the (003) x-ray diffraction peak of an ionassisted LiCoO₂ film fabricated according to the teachings of thepresent invention and a conventionally magnetron sputtered LiCoO₂ film.Both spectra are for as-deposited films. The ion assisted LiCoO₂ film inthis spectrum is the same as the “c” sample shown in FIG. 10. Thesputtered LiCoO₂ film was fabricated in an MRC 8667 using 1200 watts RFpower, 10% O₂ in Argon, 80 sccm total gas flow (8 sccm O₂ and 72 sccmAr), 20 mTorr pressure, with the substrate table grounded. Filmthickness of the sputtered LiCoO₂ film is 5460 Angstroms. Thesignificantly sharper peak for the ion-assisted film indicates thehigher degree of long range order in this film. The peak width for thisfilm is approaching that obtained by high temperature annealing of asimilar conventionally magnetron sputtered film and exceeds thatachieved for 300 degree Celsius annealed films of LiMn₂O₄. Accordingly,the LiCoO₂ film fabricated according to the teachings of the presentinvention provides a higher degree of order than conventional LiCoO₂films without resorting to a post deposition anneal step to provide thedesired crystal structure in the film. This results in significantmanufacturing efficiencies.

FIG. 12A shows a X-ray diffraction spectra of a LiCoO₂ layer fabricatedaccording to a conventional method of magnetron sputtering without thesubsequent anneal step. The magnetron sputter was performed in MRC8667sputter, with 1200 W of RF power, in an environment of argon with 10%oxygen and 80 sccm total gas flow, at a pressure of 20 mTorr. Theresulting film thickness is 5460 Angstroms. The x-ray peak full width athalf maximum (“half height width”) of the peak at 19 degrees of thisconventional sample is 2.61 degrees. The half height width is a measureof the crystallite size, which can be calculated from this data asaccording to known formulas. The crystallite size for thisconventionally magnetron sputtered film is 34 Angstroms. Thisconventional film must be annealed at high temperature to achievesufficient crystallite size to have adequate electrical properties suchthat the film is part of a functional and practical battery.

In other conventional film materials, like LiMn₂O₄, nanocrystallinestructures have been sputtered into films and prior to their anneal theyhave a crystallite size of about 40 Angstroms to about 50 Angstroms.Annealing this film at a temperature of about 300 degrees Celsiusproduces a crystallite size of about 130 Angstroms to about 160Angstroms. In some embodiments of the present invention, thesecrystallite sizes are achieved at the time of deposition. Moreover, insome embodiments, superior crystallite sizes are achieved at the time ofdeposition.

FIG. 12B shows an X-ray diffraction spectrum for a LiCoO₂ filmfabricated according to the teachings of the present disclosure.Specifically, this film was deposited using a first source and asecondary source of energized ions as discussed above with respect tosamples “b” and “c” of FIG. 11. The peak for the ion assisted depositionfilm is significantly higher than the non-assisted spectra of FIG. 12A.This indicates a higher degree of long range order in the ion assisteddeposition film. The half height width of the peak of the ion-assistedfilm at 19 degrees is 0.45 degrees. The crystallite size is 242Angstroms. Accordingly, the present fabrication techniques yield an asdeposited film having a crystallite size of greater than seven timesthat of the conventional deposition methods without post-depositionanneal. Moreover, the present fabrication techniques yield a superiorcrystallite size even when compared to the conventional film after ithas been annealed. The present fabrication technique yields a factor ofcrystallite size improvement of about a 1.8 to about a 2.6 over theconventional technique. Consequently, the present fabrication method canthus achieve superior crystallite size in the film as they are depositedresulting in faster, more efficient fabrication of thin-film batteries.Such an improved crystallite structure is highly desirable in thecathode film due to the limitations imposed on energy storage inthin-film batteries due to cathode film performance.

Another aspect of the present fabrication method is the ability tofabricate thin films at essentially room temperature with a crystallineorientation that is essentially perpendicular to a boundary withadjacent films and crystallite size. Ions must travel through theseboundaries to charge and discharge the battery. The boundaries include afirst boundary that is between the cathode film and the electrolyte filmand a second boundary that is between the electrolyte film and the anodefilm. The crystallite orientation is preferably perpendicular to theboundary planes. That is, the lithium ion lattice planes are parallel tothe lithium ion direction of travel during charging and discharging thethin-film battery. This orientation lowers the internal batteryresistance and lowers capacity loss at high discharge rates. Thecrystallite size is preferably large, e.g., over 100 Angstroms, and morepreferably over 200 Angstroms. The larger the crystallite size improveselectrical properties. Crystallite size is strongly correlated to theion diffusion coefficient, a measure of how freely lithium ions can beadded to, or extracted from the intercalation material.

While the above-described embodiments focus on lithium-intercalationmaterials and, more specifically, LiCoO₂, it will be recognized that thesome embodiments are adaptable to other intercalation materials forproducing energy-storage devices. Other types of intercalation materialinclude LiMn₂O₄, V₂O₅, and carbonaceous materials, lithium, lithiumalloys, oxides, and nitrides

Using the fundamental teachings herein, i.e., the in situ assist of thegrowing film with appropriate energy and/or species of ionized gasses,processes involving the manufacuture of photovoltaic panels,supercapacitors/ultracapacitors, and fuel cells could be made morerobust and efficient. A corresponding cost, fabrication efficiency, andperformance advantage can be gained.

For example, Solid Oxide Fuel Cells (SOFC) require the manufacturer todeposit a ceramic material on a support sturcture. See U.S. Pat. No.6,007,683, incorporated herein by reference. This ceramic is then coatedwith a conductive material such as platinum, which is the catalyst forthe fuel cell. The cost of these materials and the efficiency with whichthey conduct the appropriate ions from one side of the cell to the otherdetermines, in large measure, the cost of manufacture and operation ofthe fuel cell. The application of the techniques described hereino to afuel cell manufacturing process would yield substantially higher qualitycatalyst with higher ionic transport capability. Moreover, the presenttechniques further provide the ability to produce a thinner catalyst byvirtue of the structural properties of materials deposited via themethods described herein. This allows lower temperature operation of thefuel cell, thus, widening product latitude.

Supercapacitor/ultracapacitor performance is also enhanced by theapplication of the present techniques. See e.g., U.S. Pat. No.5,426,561, incorporated herein by reference. High energy density andhigh power density ultracapacitors and supercapacitors are improved byreduction in crystalline defects and improvement in the growth mechanismsuch that the electrolyte layer could be significantly thinned. Thisthinning improves the volumetric energy density of the device. Theimproved crystal sturcture enhances the voltage stability of theelectrolyte.

While some of the above embodiments include an ion source for providingthe focused energy to arriving adatoms at a surface of a substrate toform films having fewer defects and/or certain crystal properties, othersource of the focused energy are within the scope of some embodiments ofthe present invention. Examples of such other sources include highintensity photo sources, lasers; short duration, high intensity (flash)heat sources, short duration plasma sources. Each of these sourcesprovides the required energy to a film and does not harm previouslydeposited layers, previously connected devices, or the susbtrate. Insome embodiments, these sources provide the energy to the adatoms asthey arrive at the surface on which the adatoms will form a film.

By way of introduction, one aspect of the invention deals with the fieldof batteries and, more specifically, to the use of a thin film batteryfor enclosures for devices and also for devices which include anintegrated battery.

FIG. 13 is an exploded perspective view of an electronic device 1000having a separate printed circuit board 1010 and a separate battery1020. The enclosure 1000 typically includes a first portion 1001 and asecond portion 1002. The first portion 1001 may also be termed as abottom portion and typically may include pegs 1011 upon which theprinted circuit card 1010 rests. The pegs 1111 are also used to positionthe printed circuit card 1010 with respect to the bottom portion 1001 ofthe enclosure 1000. In addition, there are typically several other setsof stops 1112, which are used to position the battery 1020 with respectto the bottom portion 1001 of the enclosure 1000. The second portion1002 will include openings 1030 and 1032. The opening 1032 may be for adisplay such as an LCD or liquid crystal display (not shown in FIG. 13).The opening 1030 is typically for an access panel 1040, which fitswithin the opening 1030. The access panel 1040 provides access to thebattery 1020. The printed circuit board 1010 includes a batteryconnector 1022, which fits over the terminals of the battery 1020. Thebattery connector 1022 provides an appropriate amount of current to theelectrical components on the printed circuit board 1010. The secondportion 1002 of the enclosure 1000 includes several plastic hooks, whichare used to mate the second portion 1002 with the first portion 1001 toform the enclosure 1000. The prongs or hooks 1050 fit withincorresponding slots 1052 on the first portion 1001 of the enclosure1000.

These enclosures are typically made of plastic, and housed within theenclosure 1000 is a separate battery 1020 and a separate printed circuitboard 1010. These particular types of devices have several problems.First of all, the whole housing or enclosure, or at least a portion ofit, has to be removed in order to replace a battery or in order torecharge a battery. The batteries 1020 typically include a gel-typeelectrolyte which can be very toxic and dangerous and, for that reason,difficult to dispose. From a manufacturing standpoint, there is a needto assemble many parts, including the separate circuit board 1010 and abattery 1020 and an LCD (not shown). These also must be accuratelyplaced within the first portion 1001 to produce a quality-lookingenclosure 1000 for the entire electrical device. Each time a separatecomponent must be placed together or into one portion or a first portionof the device requires an additional process step. In addition, matingthe second portion 1002 of the enclosure 1000 with the first portion1001 is still a further process device. From a manufacturing point, itwould be advantageous if there were less process steps involved inmanufacturing an electronic device such as the one shown. With lessmanufacturing steps, the device can be made more simply and more costeffective.

Still a further disadvantage is that the separate components, such asthe separate printed circuit card 1010 and the separate battery 1020,require a lot of space in terms of the enclosure. The tendency thesedays is to form electronic products or electronic devices that save onspace. In most instances, a smaller electronic device is better than alarger electronic device. Therefore, there is a need for a process thatcan reduce the number of process steps and save on space and yet producea reliable battery and circuit for an enclosure.

The above-described method (see FIGS. 1–12) for placing a battery onto asubstrate can be used in many different ways in devices to produce amore compact and reliable electronic package having a battery which iscapable of being recharged a very large number of times. The batteriesand electronics could be placed directly onto an enclosure portiontherefore saving space. As a result, the design of the variouselectronic devices could be smaller than corresponding devices that arecurrently used.

FIG. 14A is an exploded perspective view of a portion of an enclosurethat includes both a battery 1110, which is deposited directly onto theenclosure portion 1100. The enclosure portion 1100 includes an interiorsurface 1101 and an exterior surface 1102. In this particularembodiment, the battery 1110 is deposited onto the interior surface 1101of the enclosure portion 1100. It should be noted that the enclosureportion 1100 resembles the first portion 1101 or the bottom portion, asshown in FIG. 13. The interior 1101 of the enclosure portion 1100 alsoincludes a plurality of traces 1120 for electrically coupling thebattery 1110 to various electronic components 1130, 1131, which areattached to sites 1140 and 1141. The sites 1140 and 1141 include theelectrical contact pads for electrically connecting the electricalcomponents 1130 and 1131 to the sites 1140 and 1141. The pads associatedwith the sites 1140, 1141 are also directly deposited onto the interiorsurface 1101 of the enclosure portion 1100. Advantageously, the battery1110 can be deposited onto the interior portion 1101 of the enclosureportion 1100 as well as the traces 1120 and the pads associated with thesites 1140 and 1141. Advantageously, in order to complete an electroniccircuit, the only process steps that need to be accomplished are to addthe electronic components 1130 and 1131. In some instances it also maybe possible to produce some of the electronic components during themanufacturing steps required to place the thin film battery 1110 ontothe interior portion 1101 of the enclosure 1100. Optionally, aprotective layer 1150 may be placed over the battery 1110 or otherselect portions deposited on the interior surface 1101 of the deviceenclosure 1100. The optional protective layer is shown in phantom and isreferenced by reference numeral 1150.

FIG. 14B is an exploded perspective view of a portion 1100 of anenclosure for an electronic device according to another embodiment ofthis invention. The enclosure portion 1100 includes an interior and anexterior surface 1102. In this particular embodiment, the battery 1110is deposited on the exterior surface 1102 of the enclosure portion 1100.The battery 1110 includes a post 1160 for the cathode and another post1162 for the anode. The posts 1160 and 1162 terminate or attach tothrough holes 1161 and 1163. The through holes 1161 and 1163 provideelectrical communication to various components located inside theenclosure portion 1100. In essence, the chief difference between theembodiment shown in FIG. 14A and the embodiment shown in this FIG. 14Bis that the battery portion 1110 is deposited on the exterior surface1102 of the enclosure portion 1100. A protective coating 1150 may beplaced over the battery portion 1110 and, more specifically, over thebattery portion 1110 and the electrical posts 1160 and 1162 and thethrough holes 1161 and 1163. The protective layer 1150 may betranslucent or may be colored to match the exterior surface 1102 of theenclosure portion 1100.

FIG. 14C is an exploded perspective view of a portion of enclosure 1103for an electronic device according to yet another embodiment of thisinvention. The enclosure portion 1103 includes a battery 1110 that isdeposited on the interior surface of the enclosure portion 1103. Theenclosure portion 1103 includes an interior portion 1101 and an exteriorportion 1102. The enclosure portion 1103 corresponds to a top portionincluding a display that can be viewed by the consumer during use. Thebattery 1110 is deposited on the interior surface 1101 of the enclosureportion 1103. Also included are traces 1120 as well as electroniccomponents 1130 and 1131. Completing the circuit is an LCD or liquidcrystal display 1170. The LCD is positioned near or at an opening in theenclosure device 1103 so that the readable portion of the LCD 1170 canbe viewed from the exterior surface 1102 of the enclosure portion 1103.Enclosure portion 1103 roughly corresponds to the second enclosureportion 1102 or on top of the electronic device shown in FIG. 13.

An addition to depositing a device or a battery device or energy device1110 onto the surface of an enclosure, another embodiment of thisinvention is to produce a sheet including multiple cells or batteries1110. The batteries 1110 are formed on a sheet of flexible or plasticmaterial 1300. It should be noted that the size of the cells 1110 andthe placement of the cells or individual batteries 1110 can be variedfor producing various different sizes and styles of formed batteries.

FIGS. 15A through 15E disclose a method whereby the battery is formedinto a conformed or conformable sheet having roughly the same shape aseither the interior or exterior surface of an electronic device. Theconformed sheet can then be placed or adhered directly to the interiorsurface or exterior surface of an electronic device. The sheet isproduced with a number or plurality of cells 1110, as will be discussedlater in this application. Once the sheet is formed as described laterin this application, the sheet 1300 is diced into individual cells orindividual battery portions 1310. In other words, a battery 1110 will beformed on a dice sheet 1310 from the main sheet 1300. The individuallydiced battery portion 1310 can then be formed into a variety of shapes,as shown by FIGS. 15C, 15D and 15E. These shapes can be any desiredshapes. In some embodiments or in most embodiments, the shape of thesheet will conform or will be able to be placed on the interior orexterior surface of an electronic device. FIG. 15C, for example, shows aroughly square battery that has folded up sides or vacuum formed sides1320. This particular device could be placed on the interior surface ofan electronic device such as a garage door opener or any other likedevice.

FIG. 15D shows a more rectangular portion or diced sheet which resultedfrom a more rectangular battery laid down upon a sheet and diced into anindividual battery portion 1310. This more rectangular formation may beglued or adhered to the inner surface of an electronic enclosure for apersonal data assistant. In the alternative, the form shown in FIG. 15Dmay also be suitable for placement on the exterior surface of anelectronic device, such as a portable data assistant.

FIG. 15E shows a more formed device that might be found on a cell phoneor similar device. FIG. 15E may be formed to fit on the interior surfaceof a cell phone or the exterior surface of a cell phone or calculator.In other words, a diced sheet 1310 is used as a starting point forvacuum forming or for otherwise forming a battery that can be attachedeither to the interior or exterior surface of an electronic device. Anelectronic device to which it is attached can be anything includinghearing aides, calculators, personal data assistants, smart cards orother credit card, watches, laser pens, power tools, surgical devices oreven catheters. The list above is not exhaustive but is merely set forthas examples of the type of the devices that may include a battery shownand formed in FIGS. 15A through 15E.

In some instances, it may be advantageous to include a battery havingmultiple cells 1110, 1110′ and 1110″. In this particular instance, adice is made 1320 that includes cells 1110, 1110′ and 1110″. The sheetcan also be formed with fold lines 1321 and 1322, as shown in FIG. 15G.

FIG. 15H shows that the batteries have been folded along the fold linesto form a stack of three batteries 1110, 1110′ and 1110″. The foldsshown in FIG. 15H are a fan fold. Once the fan fold is formed, as shownin FIG. 15H, the fan folded battery, including three cells 1330, can beformed in any desired shape, such as square-sided shape 1503 of FIG.15C, angle-sided shape 1504 of FIG. 15D and curve-sided shape 1505 ofFIG. 15E. The three-celled or multi-celled unit 1330 can be adhered tothe interior or exterior surface of any electronic device, as discussedabove. It should be noted that the fan fold can include more than threebatteries or less than three batteries. The inventive aspect is that itincludes a plurality of batteries. The cells 1110, 1110′ and 1110″ canbe attached to one another so that the cells are in series after theyare diced. Another possibility is that the electrical contacts for eachof these could be put in contact with one another as a result of fanfolding the multi-celled unit 1330.

FIGS. 15I, 15J and 15K show yet another embodiment of the invention. Inthis particular embodiment of the invention, the sheet of electricalcells 1300 includes a plurality of cells including 1110 and 1110′. Theentire sheet 1300 is then vacuum formed to form more or less an eggcarton 1350 with individual battery cells 1110 and 1110′ being formedwithin well 1360 and 1362 in the sheet 1300. Between the wells 1360 and1362 is a living hinge 1370. The batteries 1110 and 1110′ are at thebottom of each well 1360 and 1362, as shown in FIG. 15K. The livinghinge 1370 is positioned between the two wells 1360 and 1362. The firstcell 1360 can be folded on top of the second well 1362 to form anelectronic device enclosure 1380, as shown in FIG. 15L. It should benoted that the size of the battery portions 1110 and 1110′ can belimited or placed so that other traces and room for other electronicdevices can be added so that a total circuit can be formed within a discenclosure. This provides for an advantage that wherein the electroniccomponent could be directly placed into the wells 1160 and 1162 at sitesformed at the same time as the batteries were deposited onto the sheet1300. After placing all the various electronics, the electronic devicecan be formed merely by dicing two of the wells 1360 and 1362 so thatthey form a top and bottom of the device enclosure 1380. All sorts ofelectronic devices could be included, including an LCD or other displaydevice. The LCD may be readable directly through a sheet if it istransparent or the sheet, or one of the wells 1360 and 1362, may beprovided with an opening that would correspond to an opening or face ofthe display of an LCD or other display device. Thus, the sheet and thedeposited battery thereon can ultimately become the exterior surface orthe enclosure for the device formed on the sheet. This has a greatadvantage in that the process steps necessary to form a device are orcan be quite easily and efficiently done in a continuous process. Thiswould lead to very efficient manufacturing of electronic devices.

FIG. 16A is a plan view of a sheet including a plurality of cells 1110according to this invention. FIGS. 16A, 16B and 16C show a way to form alaminated battery cell and possibly laminated battery cell andelectronics for a smart card or other invention that includes a batteryand electronics within a card. The sheet 1300 shown in FIG. 16A includescells 1110. The sheet also includes fold lines 1390 and 1392. The sheet1300 is diced into individual sections, which include fold lines 1390and 1392, as well as a battery cell site 1110. The battery cell sitemight also include electronics that are also deposited with the batteryor energy source onto the sheet 1300. The diced portion 1400 includesone portion including the cell 1100 and two blank portions 1402 and1403. The diced portion 1400 is then fan folded, as shown in FIG. 16C.Once a fan fold has been formed, the cell portion 1110 is capturedbetween the two unpopulated sheet portions 1402 and 1403 and willprovide an extra protective layer. The excess portions of the sheet 1300can be trimmed, as shown in FIG. 16D to produce a smart card or cardincluding both a battery 1110 and electronic, as shown as item 1600E inFIG. 16E.

FIG. 17 is an exploded perspective view of a diced portion of a sheet1300 which includes one battery cell 1110 rolled around an electricalmotor 1500. In this case, the diced portion, which includes a cell 1110,is an elongated strip 1510 from the original sheet 1300. The elongatedstrip 1510 may include several batteries placed in series or oneelongated battery that is laid down as a strip on the sheet 1300. Theelectrical motor is electrically connected to the anode and cathode ofthe battery and then rolled on to the electrical motor 1500. In thiscase, the strip 1510, on which the battery has been deposited, becomesthe case for the electrical motor or also can be viewed as being a partof the case of the electrical motor. The electrical motor can beprovided with a sprocket 1520 that is used to drive another gear 1530having a shaft 1532 attached thereto. As shown in FIG. 17, a chuck 1540is placed upon the shaft 1532 to form a drill or other power tool.Advantageously, the power tool could be light and compact, as well asbeing capable of being recharged a multiplicity of times. The power toolcould be a hand-held drill for homeowner use or a smaller device, suchas a Dremel-brand rotary hand tool.

FIGS. 18A, 18B, 18C and 18D show several other embodiments of an LEDlight device in which the diced portion of a sheet 1300 becomes theoutside case for the penlight or light device.

FIG. 18A is a planned view of a diced battery cell 1600 which includes abattery or energy device 1110 and a switch 1602 and an LED 1604. Theswitch 1602, battery 1110 and the LED 1604 form a flashlight or LEDlighting device. The sheet, including the diced battery cell and LED, isrolled across its shorter distance starting at the end including the LED1604. The LED is merely rolled into the battery and the battery isformed around the first roll to form a spiral, as shown in FIG. 18B.

FIG. 18B is a perspective view of the diced battery cell and LED afterit has been formed into a lighting device in which the sheet 1600 inwhich the battery is deposited becomes an outer case. The LED can beactivated by enabling the switch 1604. By enabling the switch 1604, theLED can be turned on. The sheet 1600 acts as an outer case of thelighting device formed 1620.

FIGS. 18C and 18D show another embodiment of the invention for alighting device. In this particular embodiment, again a strip 1600 isprovided with a switch 1602 and an LED 1604. In this particularembodiment, the LED is positioned so that it extends beyond the lengthof the sheet 1600. In this particular embodiment, the sheet 1600 isrolled along its longer dimension around the LED 1604 to form anelongated case having the LED 1604 at one end of the case and a switch1602 at the other end of the case. This forms a light emitting diodelight 1630 in which the sheet 1600 is part of the case.

FIGS. 19A, 19B and 19C, in some instances, is necessary to keep thebattery portions 1110 and 1110′ of a power source or energy source flatand not curved when it is formed.

FIG. 19A shows a sheet 1300 which includes a plurality of individualcells such as 1110 and 1110′ which are an elongated strips and includefold lines, such as 1710. FIG. 19B is a plan view of a diced strip 1700including a plurality of battery cells 1110, 1110′ and 1110″. It shouldbe noted that the battery cells 1110″, which are located near one end ofthe strip 1700, are smaller than the battery cells formed at the otherend of the strip 1700. For example, battery cell 1110″ has a very thinwidth while the battery cell 1110 is roughly more rectangularly shaped.The strip 1700 is folded successively along fold lines 1710 to form abox of cells, as shown in FIG. 19C. The smaller cells 1110″ are in theinside or inner core of the box while the larger cells 1110 form theouter sides of the box. Each of the cells 1110, 1110′ and 1110″ and thecells in between those particular cells are placed in series with oneanother. The end result is a cubically formed battery cell 1720, asshown in FIG. 19C.

FIG. 20 is a cutaway side view of an enclosure portion that includes asheet having a plurality of battery cells. It should be noted that wehave discussed thus far that a sheet of battery cells, such as the oneshown in FIG. 15H, can either be placed on the outside surface of anenclosure or on the inside surface of an enclosure or it can be formedor deposited upon an inside or outside surface of the enclosure. FIG. 20shows that an enclosure portion 1800 having an interior surface 1801 andan exterior surface 1802 can be injection molded around a battery formedon a sheet. The battery could be a single battery, as is shown in FIG.15B, or it could be a multi-celled battery, as shown in FIG. 15H. Inother words, a sheet 1820 including one or more, or at least one batterycell 1110 formed by the above methods, could be held within a mold and asuitable plastic could be injection molded about or around the batterycell 1820. The mold could also include pins that electrically connectthe battery 1820 to the interior surface 1801 of the enclosure portion1800. The pins are shown by reference numerals 1821 and 1822.

FIG. 21A is a flow chart that depicts a process for recycling deviceenclosure portions or for recycling batteries 1110 or battery cells1110. Because the battery cell 1110 and batteries made from a number ofthese battery cells 1110 can be recharged many, many times, it iscontemplated that any electronics associated with this circuit maybecome obsolete over time and, therefore, a method of recycling thebatteries is also part of this invention.

The first step, depicted by reference numeral 1900, is to determine ifthe electronics within a circuit are obsolete. Electronics are typicallyobsolete due to technology advances in the electronics, which may occurover a number of years. If the electronics are obsolete, then thebattery 1110 or series of cells 1110 may be removed from a device coveror enclosure portion, as depicted by reference numeral 1910. The nextstep is to replace the old electrical components with new electricalcomponents, as depicted by reference numeral 1920. This first process isuseful for enclosure portions where the battery or number of cells 1110cannot be easily removed from the enclosure portion.

A second process is shown in FIG. 21B. The second process shown in FIG.21B is useful for devices in which the battery 1110 may be removedeasily from the enclosure portion. As before, the first step, depictedby reference numeral 1930, is to determine if the electronics areobsolete. If they are, the battery 1110 is merely removed from the casefor the enclosure portion and recycled for use in another enclosureportion having a similar contour, as depicted by reference numeral 1950.

In some embodiments, multiple cells are stacked in the original device,the manufacture method would include connection tabs that are coupledtogether to form the appropriate cell capacity and voltage for someparticular electronic device. Upon reaching the end of the device'slife, such battery stacks could have the tabs clipped or otherwisedisconnected from each other so that the battery stack could bedisassembled and re-assembled in a different capacity/voltageconfiguration.

Design and Fabrication of Solid-State Power Sources Cofabricated withSolid-State Integrated Circuitry

FIG. 22A shows a schematic circuit of an embodiment of a device 2200having an integrated battery 2320 and circuit 2330 sharing a commonterminal 2318. In other embodiments, more than one terminal is commonbetween battery 2320 and circuit 2330, for example, when battery 2320includes a stack having plurality of series-connected cells, and circuit2330 connects to two or more different taps in the cell stack (e.g., ifeach cell of a two-cell stack provided an open-circuit potential of 3.6volts, circuit 2330 could connect to the top of the cell stack for aportion of its circuitry needing 7.2 volts, and also to a center tap ofthe cell stack for a portion of its circuitry needing 3.6 volts, or asplit voltage battery supply could be wired to provide a groundconnection at the center tap and plus and minus 3.6 volts at the top andbottom of the stack). Common terminal 2318 connects battery 2320 tocircuit 2330, and optionally can be brought out as a connection to othercomponents. In some embodiments, common terminal connects the cathode ofbattery 2320 to circuit 2330; in other embodiments, terminal 2318connects the anode of battery 2320 to circuit 2320 as shown in FIG. 22A.In some embodiments, circuit 2330 includes one or more conductors 2317that are used to connect to other components and/or to the otherconnections to battery 2320. In some embodiments, battery 2320 includesone or more conductors 2319 that are used to connect to other componentsand/or to the other connections to circuit 2330. In other embodiments,terminal 2317 of circuit 2330 is connected directly to terminal 2319 ofbattery 2320 to form a complete device, and no connection is made toother external devices using terminals 2317, 2318, or 2319. Note thatcircuit 2330 can include any type of circuitry, for example, as shown inFIGS. 23–26, wiring traces 2332–2337, one or more active or passivedevices such as integrated circuit 2340, switches, light sources, LCDdisplays, photovoltaic cells, etc.

FIG. 22B shows a block diagram perspective view of an integrated device2201 implementing circuit 2200 of FIG. 22A having the circuit 2330 builton the battery 2320. According to the present invention, in someembodiments such as shown in FIG. 22B, battery 2320 is deposited orfabricated first (for example, onto a polymer substrate), and latercircuit 2330 is deposited or fabricated to a surface of battery 2320. Insome embodiments as shown in FIG. 22B, a top surface of the deviceimplementing circuit 2330 includes one or more conductors 2317 that areused to connect to other components and/or to the other connections tobattery 2320. In some embodiments, a bottom surface of battery 2320includes one or more conductors 2319 that are used to connect to othercomponents and/or to the other connections to circuit 2330. In someembodiments, a top surface of battery 2320 (the surface fabricatedadjacently to circuit 2330) is partially exposed and includes one ormore conductors 2318 that are used to connect to other components and/orto the other connections to circuit 2330. FIG. 23 and FIG. 24A show someexamples of devices 2300 and 2400 that are exemplary embodiments ofdevice 2201 of FIG. 22B.

FIG. 22C shows a block diagram perspective view of an integrated device2202 implementing circuit 2200 of FIG. 22A having the battery 2320 builton the circuit 2330. According to the present invention, in someembodiments such as shown in FIG. 22C, circuit 2330 is deposited orfabricated first (for example, an integrated circuit chip built onto asilicon substrate), and later battery 2320 is deposited or fabricated toa surface of battery 2320. In some embodiments as shown in FIG. 22B, atop surface of the device implementing circuit 2330 is left partiallyexposed and includes one or more conductors 2317 that are used toconnect to other components and/or to the other connections to battery2320. In some embodiments, a top surface of battery 2320 includes one ormore conductors 2319 that are used to connect to other components and/orto the other connections to circuit 2330. In some embodiments, a topsurface of circuit 2330 (the surface fabricated adjacently to circuit2330) is partially exposed and includes one or more conductors 2318 thatare used to connect to other components and/or to the other connectionsto circuit 2330. FIG. 25A and FIG. 26A show some examples of devices2500 and 2600 that are exemplary embodiments of device 2202 of FIG. 22C.

FIG. 22D shows a schematic circuit 2205 of an embodiment of anintegrated battery 2320 and circuit 2330 each having separate,electrically isolated terminals. Such embodiments are substantiallyidentical to the embodiments of FIGS. 22A, 22B, and 22C, except that aninsulator between terminal 2318 of the battery 2320 and terminal 2316 ofthe circuit 2330 keeps these electrically separate.

FIG. 22E shows a block diagram perspective view of an integrated device2206 implementing circuit 2205 of FIG. 22D having the circuit built onthe battery. Such embodiments are substantially identical to theembodiments of FIG. 22B except that an insulator 2331 is deposited onbattery 2320 before the rest of circuit 2330 is deposited or fabricated.In some embodiments, a portion of the top surface of battery 2320 isleft partially exposed and includes one or more conductors 2318 that areused to connect to other components and/or to the other connections tocircuit 2330. In some embodiments, a portion of the top surface ofinsulator layer 2331 is coated with a conductor and is left partiallyexposed and includes one or more conductors 2316 from circuit 2330 thatare used to connect to other components and/or to the other connectionsto battery 2320.

FIG. 22F shows a block diagram perspective view of an integrated device2207 implementing circuit 2205 of FIG. 22D having the battery 2320 builton but insulated from the circuit 2330. Such embodiments aresubstantially identical to the embodiments of FIG. 22C except that aninsulator 2331 is deposited on circuit 2330 before the rest of battery2320 is deposited or fabricated. In some embodiments, a portion of thetop surface of circuit 2330 is left partially exposed and includes twoor more conductors 2316 and 2317 that are used to connect to othercomponents and/or to the other connections to battery 2320. In someembodiments, a portion of the top surface of insulator layer 2331 iscoated with a conductor and is left partially exposed and includes oneor more conductors 2318 from battery 2320 that are used to connect toother components and/or to the other connections to circuit 2330.

FIG. 22G shows a block diagram perspective view of an integrated device2203 implementing circuit 2200 of FIG. 22A having the battery 2320 andthe circuit 2330 built side-by-side on a substrate 2310. In someembodiments, a pattern of conductive areas or traces is deposited onsubstrate 2310, and the successive layer(s) of battery 2320 and circuit2330 are then deposited. In some embodiments, circuit 2330 consists onlyof these conductive traces. In other embodiments, one or more of theprocess steps or deposited layers of battery 2320 and circuit 2330 arecommon, and thus performed at substantially the same time for bothcircuit 2330 and battery 2320, thus increasing the reliability, speedand yield of fabrication and lowering the cost of fabrication. In theembodiment shown, trace 2318 is deposited on substrate 2310 and forms acommon bottom electrical connection for both circuit 2330 and battery2320. Other aspects of FIG. 22G can be understood by reference to FIGS.22A–22C.

FIG. 22H shows a block diagram perspective view of an integrated device2208 implementing circuit 2205 of FIG. 22D having the battery 2320 andthe circuit 2330 built side-by-side on a substrate 2310. This embodimentis substantially identical to that of FIG. 22G, except that separatetraces are provided for signals 2316 and 2318.

FIG. 23 shows a perspective view of an embodiment 2300 of the presentinvention having a battery 2320 overlaid with circuitry. In someembodiments, substrate 2310 is a conductor such as a thin sheet ofmetal, and is overlaid with an insulator layer 2312, and then the bottomconductor layer 2322 of battery 2320. In other embodiments, insulatorlayer 2312 and bottom conductor layer 2322 are omitted, and a conductivesubstrate 2310 itself forms the bottom conductive layer for battery2320. In some embodiments, battery 2320 is a thin-film battery depositedby a process, and having a structure, as described in FIGS. 1B to 8herein. In the embodiment shown, battery 2320 includes a bottomconductive layer/electrical contact 2322 and a top conductivelayer/electrical contact 2324, and is covered by aprotective/electrically insulating layer 2331 having one or moreopenings or vias for electrical connections, for example, a via throughwhich pad/trace 2332 connects to battery 2320. In some embodiments, thetop conductor 2324 of battery 2320 is the anode connection. In theembodiment shown, the connection to the lower conductivelayer/electrical contact 2322 from pad/trace 2334 is a conductive tracedeposited over the side of battery 2320 to extended contact area 2333.In some embodiments, additional connection pads/traces 2335, 2336, and2337 are deposited, for example, using a shadow mask that defines wherethe traces will go, and a metal-evaporation source, PVD source, CVDsource, sputter source or other source to supply the conductor beinglaid down. In other embodiments, a conductive layer for circuit 2330 isdeposited over an entire upper surface, and the unneeded portions areremoved, for example, using photolithography and etching techniques. Insome embodiments, multiple layers are successively deposited, whereinthese layers include conductors, insulators, semiconductors (e.g.,polysilicon or polymer semiconductors), electrolytes, passivationlayers, mechanical-protection layers, sealants, reactants (such assensor materials that react with, e.g., smoke, carbon dioxide,antibodies, DNA, etc.) and/or decorative pattern, topography, design orcolor layers.

Some embodiments further include a separately fabricated circuit 2340that is bonded (e.g., by adhesive or solder) to the rest of thedeposited circuitry 2330, for example, a flip-chip integrated circuit2340 having bump, ball or ball-grid array connections 2341 as shown inFIG. 23. In other embodiments, packaged chips are used, e.g., J-leaded,gull-wing leaded, in-line-pin, or other plastic-or ceramic-encapsulatedchip packages.

FIG. 24A shows a perspective view of an embodiment 2400 of the presentinvention having a battery 2320 overlaid with an integrated device 2430.In some embodiments, integrated device 2430 is a so-calledsupercapacitor relying on either charge accumulation on opposing sideson an insulator (as in a capacitor) or ion transport across anelectrolyte (as in a battery), or both charge accumulation and iontransport to store electrical energy. In some embodiments, integrateddevice 2430 includes a photovoltaic cell of conventional constructiondeposited directly on battery 2320.

Some embodiments further include a separately fabricated circuit devicesuch as an integrated circuit chip 2440 that is wire-lead bonded todevice 2430 using wire 2441, to device-battery common terminal 2324using wire 2443, and to bottom battery contact 2322 using wire 2442. Forexample, in one embodiment having a supercapacitor device 2430,integrated circuit 2440 includes a wireless communication circuit thatuses the battery for overall power needs and uses supercapacitor device2430 for quick-burst power needs such as for transmitting short burst ofdata to an antenna. Other embodiments include other fabricated circuitdevices such as switches, LEDs or other light sources, LCD displays,antennas, sensors, capacitors, resistors, etc., wired to device 2400.

In one embodiment, battery 2320 includes a bottom conductor layer ofplatinum (e.g., 0.5 micrometers thick), a cathode of lithium cobaltoxide covered by a LiPON electrolyte and a carbon anode, and a topelectrode of platinum. On top of these depositions, device 2430 includesa layer of ruthenium oxide, an electrolyte of LiPON, another layer ofruthenium oxide and a top layer of platinum. Such a device 2430 wouldstore energy by transporting lithium ions derived from the LiPONelectrolyte from one to another of the top and bottom surface of theelectrolyte, as well as perhaps moving charge (electrons) to an opposingsurface. Such a device exhibits a higher-current discharge rate than acomparable battery, and a higher energy storage than a comparablecapacitor. The present invention including ion-assist depositionprovides for higher quality cathode films (better crystal orientation)and better electrolyte films (more complete isolation and fewer pinholedefects for any given thickness, thus allowing thinner electrolyte filmsthat increase ion transport rates), and better capacitor dielectricfilms (more complete isolation and fewer pinhole defects for any giventhickness, thus allowing thinner dielectric films that increasedielectric isolation, capacitance, and charge storage). In someembodiments, a capacitor insulator layer is made of a barium strontiumtitanate.

In some embodiments, a cathode layer of lithium-cobalt-oxide is coveredby a LiPON electrolyte layer and a lithium(0.5)-cobalt-oxide anodelayer. This anode layer is non-stoichiometric deposited using a sourcethat has excess cobalt and oxygen relative to lithium as compared tothat used for the cathode, and various embodiments use different lithiumratios.

Design and Fabrication of Solid-State Power Sources Fabricated as aLaminate on a Rigid or Flexible Direct Energy Conversion Material suchas Photovoltaic

Virtually all electronics require energy to operate and perform thedesigned functions. This energy typically comes from either an AC sourcesuch as a home wall electrical outlet or a battery mounted in thepackaging of the electronic device. More recently, advances in theconversion of heat and light into energy have fueled research in thearea of direct energy conversion (e.g., by photovoltaic cells). This hasthe potential to supply a large percentage of the world energy needs ina clean and safe manner. One problem with these methods of energy supplyhas been the cyclical nature of the energy being converted. Whether heator light, the source usually goes away for a 6-to 12-hour periodresulting in zero output from the unit. One way around this problem isto supply a battery with the unit to supply power during periods of lowlight or heat input. This is however not an ideal solution as today'srechargeable batteries are bulky and failure prone after severalcharge/discharge cycles. The present invention solves this problem byintegrating its solid-state Lithium battery directly on the energyconversion substrate. The present battery has a distinct advantage overcurrent technologies, in that it is not prone to failure or memoryproblems over tens of thousands of charge/discharge cycles, has veryhigh capacity, is lightweight, can be fabricated on nearly any substrateand is cheap to manufacture. The resultant product is a reliable,portable power source with steady output over extended periods or rainor shine, night or day, warm or cold.

According to the present invention, solid-state processes are used tocofabricate direct energy conversion materials and energy storage on thesame substrate. This is possible by using the low-temperature processesfor solid-state batteries described above.

FIG. 24B shows a block diagram of a battery-layer-deposition system2460. In some embodiments, system 2460 includes a supply reel 2461, adeposition chamber 2462 that deposits one or more layers of battery 2320onto a substrate 2410 as described above, and a takeup reel 2463.Typically, deposition chamber 2462 is a vacuum chamber that enclosessupply reel 2461 and takeup reel 2463, and successively deposits aplurality of layers, wherein each of one or more of the layers isimmediately treated (e.g., by ion assist, laser surface anneal, heatsurface anneal, or kinetic treatment), according to the presentinvention, to impart a high-quality surface structure to that layer orthose layers before subsequent layers are deposited, and withoutsubstantial heating of the underlying layer(s) or substrate. For layersthat need to be thicker, a longer deposition station is provided thanthe station for thinner layers. In some embodiments, the lower contactlayer 2322 is deposited onto a starting substrate film, fabric, or foil2410, then the cathode, electrolyte, anode, and anode-contact layers aredeposited, wherein the cathode layer and/or the electrolyte layer aretreated (e.g., by an ion-assist beam) before subsequent layers aredeposited.

FIG. 24C shows the resulting item 2464, which is a continuous sheet ofsubstrate material 2410 having batteries 2320 deposited on it. Thispartially built item 2464 is then used as the supply reel 2466 oflayer-deposition system 2465 of FIG. 24D.

FIG. 24D shows a block diagram of a energy-conversion-layer-depositionsystem 2465. In some embodiments, system 2565 deposits layers that forma photovoltaic cell 2430 onto battery 2320 of FIG. 24A. In someembodiments, system 2460 and system 2465 are merged into a single systemhaving a single supply reel 2461 and a single takeup reel 2468, andhaving layers of the battery 2320 and of the photovoltaic cell 2430successively deposited. In other embodiments, other types of devices2430 are deposited such as capacitors, antennae, circuitry, transducers,sensors, magneto-resistors (e.g., of the giant magneto-resistor type),etc.

FIG. 24E shows a perspective view of a processed sheet 2469 that is theresult of processing be system 2460 and system 2465. Sheet 2469 is thencut or diced into individual devices 2400. FIG. 24F shows a perspectiveview of three diced final devices 2400. In other embodiments, sheet 2469is cut into any desired number of devices 2400.

In other embodiments, system 2460 and system 2465 deposit a battery 2320and a photovoltaic cell 2330 side-by-side on one face of substrate 2310,such as shown in FIG. 22G and FIG. 22H. In some such embodiments, one ormore of the layers deposited for battery 2320 are also deposited forphotovoltaic cell 2330 simultaneously of the same deposition material,thus saving process steps but making a wider device than if stacked asin FIG. 24A.

FIG. 25A shows a perspective view of an embodiment 2500 of the presentinvention having an integrated circuit 2510 overlaid with a battery2320. In some embodiments, integrated circuit 2510 includes a topinsulator layer 2511 having a plurality of vias or openings 2512 to theactive surface of the integrated circuit 2510 (the side with devices andconnectors). Two of these vias are used as contacts 2514 and 2515between integrated circuit 2510 and battery 2320. Battery 2320 isdeposited as described for FIG. 23. In some embodiments, battery 2320 isdeposited on an integrated circuit wafer before integrated circuit 2510is diced apart from the other integrated circuits. In some embodiments,battery 2320 is deposited onto integrated circuit 2510 after integratedcircuit 2510 is diced apart from the other integrated circuits. Someembodiments further include a passivation layer over the top and sidesof battery 2320 such as layer 2331 of FIG. 23.

In other embodiments, a circuit such as circuit 2330 of FIG. 23 is usedin place of integrated circuit 2510 of FIG. 25A. Thus, a pattern of viasand/or other devices or circuitry is deposited on a substrate, andbattery 2320 is deposited on the top of the predefinedcircuitry/substrate, as in FIG. 25A. In some embodiments, a photovoltaiccell is used as such a circuit device/substrate, and battery 2320 isdeposited directly on the premanufactured photovoltaic cell. In someembodiments, an integrated circuit such as 2440 of FIG. 24A is wired tothe battery 2320 and the premanufactured photovoltaic cell to controlcharging of the battery from the cell and/or to control using power forother devices (such as a light source or hearing aid) from the photocellduring periods of high amounts of light and power available from thephotovoltaic cell, and using power from the battery during periods oflittle or no light and power available from the photovoltaic cell.

Virtually all electronics require energy to operate and perform thedesigned functions. This energy typically comes from either an AC sourcesuch as a home wall electrical outlet or a battery mounted in thepackaging of the electronic device. Until the last few years, thisapproach has proved to be acceptable even though the inefficienciescaused waste of both energy and natural resources in that the devicehousing had to be made large enough to incorporate the energy package orconversion electronics. As electronic complexity increases, the wastedreal estate and energy begin to become an issue as the demands ofoperator interface begin to compete with the energy source for area onthe device. The application of the solid-state battery process of thepresent invention allows the cofabricating of electronics and theassociated power source together on chip.

Solid-state processes are used to cofabricate electronics andsolid-state rechargeable battery on a common substrate such as siliconused for IC processing. This is possible by using the low-temperatureprocesses for solid-state batteries described above.

Referring to FIG. 25A, in some embodiments, the integrated circuit (IC)2510 in wafer form is processed normally through final passivationincluding bond-pad etch. All thermal processing necessary for theelectronics is performed conventionally. The IC in wafer form is sent tobackend energy processing. In some embodiments, the design of the ICincludes electronics for control of recharge for the solid-state energysource; contact vias for connecting the cathode plate and anode plate tothe circuit. Using shadow masks with sufficient overlay accuracy, thenecessary components of the energy structure 2320 are deposited usingPVD or CVD as described above. A final passivation coating (such as 2331of FIG. 23) is applied to the energy stack. The IC in wafer form withenergy source integrated is sent for test, dicing and packaging. Thisprovides integration of electronics and solid-state rechargeablebatteries by cofabrication.

Design and Fabrication of Solid-State Power Sources Fabricated as aLaminate on the Packaging for the Device the Energy Source Will Power

Solid-state processes are used to cofabricate electronics and packaging.This is possible by using the low-temperature processes for solid-statebatteries described above.

FIGS. 25B–25E show a fabrication sequence for cofabrication ofsolid-state integrated circuits and solid-state energy source such asthat described above, but onto a packaged IC 2540. FIG. 25B shows a planview and FIG. 25C shows an elevational view of IC 2540. In someembodiments, IC 2540 includes a silicon chip 2545 having integratedcomponents such as transistors, resistors, memory, etc., a lowersubstrate 2546, and a wiring superstrate 2544 having deposited wires2543 that extend to bonding vias 2542. FIG. 25D shows a plan view andFIG. 25E shows an elevational view of an integrated battery-IC 2501.Battery-IC 2501 includes a cathode 2326 (e.g., lithium cobalt oxide),electrolyte layer 2327 (e.g., LiPON), and anode layer 2328 (e.g.,including copper, carbon, lithium, lithium-magnesium, and/or othersuitable anode material). Passivation overcoat layer 2329 suitable toprotect the inner components of battery 2320 is then deposited or grown.

In one embodiment, the packaged IC 2540 product is formed byconventional means. All machine work and cleaning is accomplished. Thepackage 2540 is sent to energy processing for deposition of battery 2320or other energy-storage device. The design of the package included asuitable area 2549 for deposition of battery components. Using shadowmasks with sufficient overlay accuracy, the necessary components of theenergy structure (e.g., a battery and/or photovoltaic cell) aredeposited using the methods described above. A final passivation coating2329 is applied to the energy stack structure. The package with energystructure integrated is sent for assembly.

In one embodiment, further electronics are attached to thepackage/energy entity 2501 by way of adhesive. The electronics are thenhardwired to the package/energy entity. In a second embodiment, theelectronics are mounted directly to the package/energy entity by 2501way of solder bumps. In some embodiments, the entire assembly isoptionally potted, then sealed by the package cover. In otherembodiments, the battery is formed on a substrate suitable as apackaging material. The substrate is formed into individual package formfactors. The package with energy structure integrated is sent forassembly.

Thus, the present invention provides integrated product packaging andsolid-state rechargeable batteries by cofabrication where the battery isdeposited on the already-formed package. The present invention alsoprovides integrated product packaging and solid-state rechargeablebatteries by cofabrication where the battery is deposited on a suitablepackage material, then formed into the package.

The present invention also provides a method of attaching electronics toa package/energy hybrid wherein the electronics are mounted withadhesive, then hardwired to the energy source. The present inventionfurther provides a method of attaching electronics to a package/energyhybrid wherein the electronics are attached to the energy source viasolder bumps.

FIG. 25F shows a block diagram of a layer-deposition system 2560 muchthe same as that of FIG. 24B, however rather than using a sheet ofpolymer or other homogenous substrate material 2410, system 2560 startswith a sheet 2561 having a plurality of processed packaged ICs 2540 thatare received by takeup reel 2563.

FIG. 25G shows a perspective view of a processed sheet 2569. Sheet 2569includes a plurality of preprocessed circuits 2540 each having a battery2320 deposited on it by system 2560. Sheet 2569 is then cut or dicedinto individual devices 2501.

FIG. 26A shows a perspective view of a device 2600 of the presentinvention having an integrated circuit 2510 overlaid on its back with abattery 2320. This embodiment is similar to that of FIG. 25A, exceptthat the battery 2320 is deposited on the back of IC 2510, and iswire-lead bonded to contact 2514 using wire 2614 from battery contact2519, and to contact 2515 using wire 2615 from battery contact 2518.

In some embodiments, device 2600 further includes device 2650 such as aphotovoltaic cell fabricated on a surface of integrated circuit 2510,for example, on the opposite side as that facing battery 2320. In someembodiments, such a photovoltaic cell 2650 provides power to IC 2510 forboth operation of IC 2510 and for charging of battery 2320 duringperiods of relatively bright light, and then battery 2320 provides powerto IC 2510 for operation during periods of relatively dim or no light.In some embodiments, device 2600 includes one or more devices 2650 suchas sound transducers for such applications as a hearing aid having ancombined transducer-battery-amplifier device. In some such embodiments,both a photovoltaic cell 2650 and one or more sound transducers 2650 aredeposited in order to provide a light-rechargeable hearing aid whichcould be taken out of the ear at night and placed in a light-emittingrecharging stand (e.g., that of FIG. 27L), avoiding the need to replacebatteries or even to electrically connect to an external rechargingcircuit. In some embodiments, a photovoltaic cell and/or a soundtransducer is/are deposited on one face of device 2600 for rechargingand for sound pickup, and a sound transducer is deposited on an opposingface for use as s speaker for applications such as a hearing aid.

In yet other embodiments, 2600 further includes device 2650 such as amagnetoresistive sensor fabricated on a surface of integrated circuit2510, for example, on the opposite side as that facing battery 2320.Such a device 2600 could be used in a compass, for example.

In some embodiments, embodiment 2600 further includes an antenna orelectromagnetic radiation receiving loop 2662 fabricated on a surface ofintegrated circuit 2510, for example, on the opposite side as thatfacing battery 2320. In some such embodiments, device 2600 also includesone or more devices 2650 such as sound transducers for such applicationsas a hearing aid having an combined transducer-battery-amplifier devicein order to provide a radio frequency-wave-rechargeable hearing aidwhich could be taken out of the ear at night and placed in anRF-emitting recharging stand (e.g., that of FIG. 27M), avoiding the needto replace batteries or even to electrically connect to an externalrecharging circuit.

In various embodiments, such an antenna or electromagnetic radiationreceiving loop 2662 is fabricated on device 2202, 2203, 2204, 2206,2207, 2208, 2300, 2400, or 2500 (or 2700 described below) or otherbattery devices described herein. In some such embodiments,electromagnetic radiation received wirelessly by antenna 2662 can besuch low-frequency radiation as 50-or 60-hertz magnetic radiation from acoil connected to house current (e.g., that of FIG. 27L). In other suchembodiments, RF radiation such as radio, TV, cellular, etc. havingfrequencies up to and exceeding 2.4 GHz is received. In someembodiments, multiple antennae are used, e.g., one for transducingcommunications signals and another for receiving recharging signals.

FIG. 26B shows a block diagram of a layer-deposition system 2660. System2660 is much the same as system 2560 of FIG. 25B, except that thebattery material is deposited on the back of the sheet, i.e., on theside opposite the active parts or connections of circuit 2510.

FIG. 26C shows a perspective view of a processed sheet 2669. Sheet 2669includes a plurality of devices or circuits 2510 each having a battery2320 on the back. FIG. 26D shows a perspective view of diced finaldevices 2600 after being dices or cut apart. FIG. 26E shows aperspective view of wired diced final device 2600 after being wired,e.g., by wires 2615 and 2616 as shown, or by deposited traces (notshown) that extend electrical connections from the top to the bottom ofdevice 2600.

In some embodiments, a roll of flexible fabric 2661 suitable for use asa substrate for direct energy conversion has deposited on it thenecessary elements and/or layers to form the desired unit (such as aphotovoltaic cell) using roll-to-roll concepts. The roll is then takento the energy deposition tool 2660 which is also configured to operatein a roll-to-roll mode. The battery 2320 is fabricated on the backside(the side opposite the active side of the device, e.g., the side havingthe light-reception face of a photovoltaic cell) of the roll. Electricalconnection is made after fabrication using hardwire techniques, such asshown in FIG. 26E.

In other embodiments such as shown in FIGS. 24B–24F, a roll of flexiblefabric 2461 suitable for use as a substrate for direct energy conversion(e.g., for a photovoltaic cell) is deposited with materials to form asolid-state lithium battery using roll-to-roll concepts in system 2460.The resulting roll 2463 is then taken to the direct energy conversionmaterials deposition tool 2465 which is also configured to operate in aroll-to-roll mode. The direct energy conversion material 2430 isdeposited directly on the solid-state battery 2320. In some embodiments,electrical connection is made through vias formed during battery anddevice fabrication such as shown in FIG. 23.

In yet other embodiments, roll 2461 above is replaced by a differentsubstrate, such as wafer 2961 of FIG. 29A described below, also suitablefor use in direct energy conversion. The fabrication tools 2960 and 2965are also configured to handle the new substrate form factor such assquare plates or round wafers.

In still other embodiments, roll 2661 above is replaced by a differentsubstrate, such as wafer 2971 of FIG. 29E below, also suitable for usein direct energy conversion. The fabrication tools 2960 and 2965 arealso configured to handle the new substrate form factor such as squareplates or round wafers.

Thus, the present invention provides a method for integratingsolid-state lithium batteries with direct energy conversion materials ona flexible fabric. Further, the present invention provides a method forintegrating solid-state lithium batteries with direct energy conversionmaterials on a rigid substrate.

FIG. 26F shows a perspective view of a hearing aid 2690 incorporating awired diced final device 2600. In some embodiments, device 2600 includesa photovoltaic cell 2650 for recharging battery 2320 the operateshearing aid 2690. In some embodiments, sound transducers of conventionalmaterials such as piezo-electric materials are deposited as layers bysystem 2660 to be used as the microphone and speaker of hearing aid2690.

FIG. 27A shows a plan view of a starting substrate 2710 of an embodimentthat will have an integrated battery and device sharing a commonterminal. FIG. 27F shows an elevation view of the starting substrate ofFIG. 27A. FIG. 27B shows a plan view of the substrate 2710 of FIG. 27Aafter deposition of the integrated battery 2320 and device 2430 sharinga common terminal. In some embodiments, integrated battery 2320 anddevice 2430 are a thin-film battery and supercapacitor having electricalconnections 2322, 2324, and 2431 such as shown and described in FIG. 24Aabove. FIG. 27G shows an elevation view of the partially built device ofFIG. 27B. FIG. 27C shows a plan view of the substrate of FIG. 27B afterplacing and wiring a separately fabricated chip 2440 connected by wires2441, 2442, and 2443 to the integrated battery 2320 and device 2430sharing common terminal 2324. FIG. 27H shows an elevation view of thepartially built device of FIG. 27C. FIG. 27D shows a plan view of thesubstrate 2710 of FIG. 27C after placing-and wiring a loop antenna 2750.FIG. 271 shows an elevation view of the partially built device of FIG.27D. FIG. 27E shows a plan view of the final device 2700 having thepartially built device of FIG. 27D after a top encapsulation layer 2760has been deposited. FIG. 27J shows a cross-section elevation view of thedevice 2700 of FIG. 27E. The elevational views of FIGS. 27E–27J are notto scale. In some embodiments, device 2700 is approximately the size andthickness of a common credit card. In some embodiments, a magnetic strip2770 and raised lettering 2780 are also fabricated on device 2700.

FIG. 27K shows an perspective view of the device of FIG. 27E at amagnetic-recharging station. In the embodiment shown, coil 2790 useshouse current to generate a 60 Hz magnetic field, and together with coil2750, form a transformer inducing current flow in coil 2750, which isrectified and used to recharge battery 2320.

FIG. 27L shows a perspective view of a device 2700 of FIG. 27E, butfurther including a photovoltaic cell 2650, at a light-rechargingstation that includes lamp 2791. In some embodiments, device 2700 isfabricated in a shape to fit in the ear, includes sound transducers, andfunctions as a hearing aid that can be recharged an indefinite number oftimes, eliminating the need to replace its battery.

FIG. 27M shows a schematic of the device of FIG. 27E at aradio-wave-recharging station 2792. Radio waves fromradio-wave-recharging station 2792 are picked up by antenna 2750, andthe received radio wave's power is scavenged to recharge battery 2320using a conventional recharging circuit, e.g., implemented in circuit2440.

Solid-state rechargeable batteries such as those described above havethe unique ability of being integrated directly with the electronicsthey will power. Further integration of thin-wire antenna/coil 2662 or2750 to be used as one of the coils of a two-part transformer such asshown in FIG. 27K and/or RF-scavenging technology such as that used inkeyless entry systems allows the recharging of the solid-state thin-filmbattery 2320 wirelessly (through the air). Using techniques alreadycommon in RF I.D. tagging, the communicated energy is converted into aD.C. voltage and used to perform functions on board. In the case where abattery already exists on board, the D.C. voltage is used to power uprecharge circuitry to wirelessly recharge the on-board battery.

Certain needs exist within industry that would benefit from theintegration of energy, storage communication and electronics on a singleplatform. One example is control of warehouse inventories where a small“credit card” is attached to an item in the warehouse. On board the“credit card” is an antenna, supercapacitor, solid-state battery and allrequired electronics. When the controller needs to know something aboutthe package, the warehouse is queried via cellular or other wirelessmeans with the I.D. of the package in question. The query “wakes up” thepackage and entices it to respond with whatever data is programmed-to bereleased. The supercapacitor discharges into the antennae-drivingcircuitry bursting the data out to the central computer. At the sametime, the electronics on the credit-card form factor device perform aself evaluation to see if any anomalies have or are occurring such as“battery needs charging.” If the answer is yes, the central computersends a signal of appropriate length to recharge the on-board batteryusing technology described herein.

Another application seeing significant enhancement from the integrationof energy, communication and electronics on a single platform is animplantable device such as a pacemaker. This technology allows a batteryhaving a very large number (if not infinite) charge/discharge cycles tobe implanted as part of a pacemaker. When a “battery-low condition” isencountered, the battery is remotely recharged through the body using ACmagnetic fields, sound or ultrasound, radio-frequency or other energysources.

Solid-state processes are used to integrate electronics, solid-staterechargeable battery, and antenna on a single platform such as a “creditcard” form factor. This is possible by using the low-temperatureprocesses for solid-state batteries and supercapacitors described.

The present invention provides a platform integrating electronics,solid-state rechargeable batteries, and antenna on a single platformsuch as a credit card or implantable device allowing remote wirelessrecharging of the on-board battery.

FIGS. 27A–27J show a fabrication sequence if some embodiments of anexample of a credit-card form factor I.D. tag with remote rechargecapability.

FIG. 31B shows a fabrication sequence for an example of an implantabledevice such as a pacemaker 3101. This method starts with a substantiallyflat sheet deposited with batteries, which is then cut apart and formedinto a three-dimensional shape. The method is otherwise similar to thatof FIG. 31C.

FIG. 31C shows one method for making a pacemaker 3102. The methodincludes a plurality of steps carrying the reference numbers 3194, 3195,3196 and 3197. The pacemaker 3102 includes a first half 3131 and asecond half 3130. In the initial step, 3194, the second half 3130 isprovided. A battery cell 1110 is formed on an interior surface of thepacemaker 3102, as shown by step 3195. The single cell 1110 is depositedon the interior surface, as shown by step 3195. The electronics 3150 arethen placed onto the battery 1110 to form a circuit with the battery1110, as depicted by step 3196. The first half 3131 of the enclosure isplaced over the second half 3130 to form the assembled pacemaker 3102,as depicted by step 3197.

Solid-state rechargeable batteries such as those described above havethe unique ability of being integrated directly with the electronicsthey will power. Further integration of thin-wire antenna and an energyburst device such as a supercapacitor would allow the device tocommunicate over large distances via any possible number of currentcommunication methods including but not limited to cellular.

This invention relates to solid-state rechargeable batteries and theintegration of such with wireless communication (antennae andelectronics), supercapacitor and conventional electronics on a singleplatform.

Certain needs exist within industry that would benefit from theintegration of energy, communication and electronics on a singleplatform. One example is control of warehouse inventories where a small“credit card” is attached to an item in the warehouse. On board the“credit care” are an antenna, supercapacitor, solid-state battery andall required electronics. This “credit card” allows tracking oflocation, time at location, description of item in question and/orinformation on the environment. When the controller needs to knowsomething about the package, the warehouse is queried via cellular orother wireless means with the I.D. of the package in question. The query“wares up” the package and entices it to respond with whatever data isprogrammed to be released. The supercapacitor discharges into thecircuitry driving the antennae bursting the data but to the centralcomputer. At the same time, the electronics on the “credit card”performs a self evaluation to see if any anomalies have or are occurringsuch as battery needs charging. If the answer is yes, the centralcomputer could send a signal of appropriate length to allow recharge ofon-board battery using technology described above.

Solid-state processes are used to integrate electronics, solid-staterechargeable battery, supercapacitor and antenna on a single platformsuch as a “credit card” form factor. This is possible by using thelow-temperature processes for solid-state batteries and supercapacitorsdescribed above.

Thus, the present invention provides for integrating electronics,solid-state rechargeable batteries, supercapacitors and antenna on asingle platform such as a credit card or implantable device.

Method of recycling and re-using solid-state lithium-ion batteries: FIG.28A shows an elevation view of a battery 2800 having stacked cells 2801.Each cell includes an anode tab 2802 and a cathode tab 2803, wherein allof the anode tabs 2802 are soldered together, and all of the cathodetabs 2803 are soldered together. Optionally, battery 2800 isencapsulated with a potting material.

FIG. 28B shows a plan view of a single battery cell 2801 afterrecycling. In some embodiments, the anode tab 2802 and the cathode tab2803 are “tinned” (covered with fresh solder) and/or solder bumped tofacilitate reassembly soldering operations.

FIG. 28C shows a process 2810 used for recycling. Process 2810 includesproviding batteries 2800 to be recycled into input bin 2820. In someembodiments, the batteries are de-potted at de-pot station 2822,de-soldered at de-solder station 2824, tested at test station 2826, andoutputted into sorted output bins 2828 based on the testing results.

Of the 2 billion rechargeable batteries consumed in the United States in1998, only about 300 million were actually recycled. That means about1.7 billion recyclable batteries made it into landfills. Although moreand more of these batteries are technically environmentally safe, thisstill represents a significant load on the landfill situation in theUSA. The present invention provides a solution that will have itsgreatest impact as solid-state lithium-ion batteries begin to dominatethe rechargeable battery market. In this invention, solid-statelithium-ion batteries have a date code and/or recycle value associatedwith them. Because of the very large (over 40,000) number ofcharge/discharge cycles possible with solid-state lithium batteries, theaverage expected life of a cell could exceed 100 years. It is thereforevery likely that the product in which the cell is placed will lose itsusefulness well before the battery cell is depleted. Thus, when thebattery reaches the end of its useful life based on the obsolescence ofthe product it was in, the consumer will be enticed to recycle thebattery based on the value returned to the consumer in exchange forrecycling. This value could be a function of the date code andapplication the battery was used in. The recycler 2810 then disassemblesthe unit 2800, tests the single cells 2801, then rebuilds the cells inwhatever configuration is most in demand at that time. The rebuilt unitcould then be sold at an appropriate cost and warranty on performance.

This invention relates to recycling of rechargeable batteries,specifically the recycling of batteries that are manufactured in such away so as to allow the disassembly of the individual battery cells uponrecycling.

For years the automotive industry has recycled certain high-costcomponents of the automobile. Using this philosophy, the presentinvention applies those principles to the recycling of rechargeablebatteries. As battery technology advances, the batteries are actuallyoutlasting the products they were designed for. The conventionalsolution is to depend on the consumer to recycle the no-longer usefulbattery by taking it to some place that will accept the battery. Thedata suggests that this is wishful thinking, as fully 80% of Americansdo not recycle their rechargeable batteries. Rather, they throw theminto the garbage and the battery ends up in a landfill. Although thenewer battery chemistries are relatively benign to the environment, thesheer bulk of the disposed batteries can represent an enormous strain onlandfills. This invention allows enticement of the consumer to recyclethe batteries by offering a cash reward, or other inducement such asreduced cost on new batteries, in exchange for recycling. Since money isinvolved, this program should be able to be implemented on a wide scalemaking participation likely.

In one embodiment, rechargeable battery manufacturers are encouraged tomanufacture their products in such a way that upon recycling, thebattery can be broken down into individual cells and these cells rebuiltinto “new” batteries. In some embodiments of the present inventionprovide such a recycling program, and provide batteries with features tofacilitate recycling, for example, marking one or more of the cells of abattery with a code indicating such information as date of manufacture,voltage, capacity, value, composition physical size, and/or weight. Anexample is a cell-phone battery having a capacity of 1000 mAh(milliampere hours). Some embodiments involve the parallel assembly ofapproximately 10 individual cells into a battery pack that would have acapacity of 1000 mAh. These individual cells are fabricated on a gridthat provides bonding tabs allowing the configuration of the cells in avariety of modes. Upon recycling, the batteries are de-potted,de-soldered and analyzed for robustness. Cells having data codes andtest results indicating substantial life remaining would be repackagedaccording to market needs. In some embodiments, recycling rechargeablebatteries involves the breaking down of the battery pack into individualcells which are tested and re-assembled into usable battery packs. Someembodiments include a method of determining the viability of recycledbattery cells for use in rebuilt batteries such as measuring thecharge-discharge voltage-current curve over one or more cycles. Someembodiments include a method of de-potting batteries such that theindividual cells are accessible and not damaged, such as using a plasticpotting compound that can later be dissolved using a solvent and/or heatthat does not deteriorate the battery. Some embodiments include a methodof disconnecting cells from the original battery pack and re-connectinginto a new configuration, such as having solder tabs that extend beyondthe battery pack so that the solder tabs can be desoldered withoutsubstantially heating the battery itself. Some embodiments include arecycling system based loosely on the system used by the automotiveindustry in rebuilding of starters, alternators etc. and the techniquesused by lead acid battery outlets.

FIG. 29A shows a block diagram of a layer-deposition system 2960. System2960 has layer deposition sections 2962 much the same as those of Figure2460 of FIG. 24B, except that it is set up to deposit layers onto wafers2961 (or onto diced ICs 2510 rather than onto flexible substrates),resulting in processed wafers 2963.

FIG. 29B shows a perspective view of a partially processed wafer 2964having battery material 2320 on wafer 2961 or IC 2410.

FIG. 29C shows a block diagram of a layer-deposition system 2965. System2965 has layer deposition sections 2962 much the same as those of Figure2465 of FIG. 24D, except that it is set up to deposit layers onto wafers2966 (or onto diced ICs 2510 rather than onto flexible substrates) bylayer-deposition sections 2967, resulting in processed wafers 2968. FIG.29D shows a perspective view of a processed sheet 2969 having batterymaterial 2320 on wafer 2961 or IC 2410 and covered by a device 2430 suchas a photovoltaic cell.

FIG. 29E shows a block diagram of a layer-deposition system 2965. Insome such embodiments, system 2965 deposits layers forming aphotovoltaic cell device 2650 onto a wafer 2971 or IC 2510. FIG. 29Fshows a perspective view of a partially processed wafer 2974. FIG. 29Gshows a block diagram of a layer-deposition system 2960. In some suchembodiments, system 2960 deposits layers of a battery 2320. FIG. 29Hshows a perspective view of a processed wafer 2979. In some embodiments,wafer 2979 represents a single device, and in other embodiments, wafer2979 is diced or cut into a plurality of individual devices and thenwired as necessary to connect the signals on the top of the device tothe bottom of the device. FIG. 29I shows a perspective view of wireddiced final device 2600 having wires 2914 and 2915.

Turning now to FIGS. 30, 31 and 32, specific examples of devices willnow be provided. FIG. 30 shows an implantable device 3000 used tostimulate specific portions of the brain. One use of such device 3000 isfor deep brain neural stimulation, for example, in order to treatParkinson's Disease. By sending signals to a specific portion of thebrain the tremors associated with Parkinson's Disease may be reduced. Inthe past, a lead or conductor was implanted in the brain so thatelectrical signals may be sent to the specific area of the brain forreducing tremors. The lead passes under the skull and through the neckto a pocket near the patient's chest in current versions. As shown inFIG. 30, after a burr hole has been made in the skull, a port 3010 isplaced in the burr hole. The port 3010 includes a cap 3012, which isused to hold the lead in place during implantation as well as afterimplantation. In this particular invention, the cap 3012 is made of asuitable biocompatible material. Imbedded within the cap is a batterycell 1110 or a series of battery cells 1110. The electronics necessaryto deliver the signals at a desired rate or programmable rate is alsoimbedded within the cap 3012. An RF antenna 3014 is also placed withinthe cap so that the battery 1110 imbedded within the cap 3012 can berecharged by passing radio frequency into the cap or inductivelycoupling the required energy into the cap. Another embodiment may usethe lead 3020 for an energizing antenna and may include a separateantenna for programming the electronics used to deliver signals to thebrain.

FIG. 31A is directed toward a pacemaker 3100. Rather than includeseparate batteries within the case of the pacemaker 3100, the enclosure,or at least one enclosure portion, includes a battery 1110 or a seriesof cells 1110. The pacemaker 3100 may include an antenna 3120 which isused to direct radio frequency toward the pacemaker for recharging ofthe battery 1110 that is positioned within the case or enclosure of thepacemaker 3100.

FIG. 31B shows the method for making the pacemaker 3101. The method iscomprised of a plurality of steps carrying the reference numbers 3190,3191, 3192 and 3193. The pacemaker 3100 includes a first half 3131 and asecond half 3130. A plurality of battery cells 1110 are formed on asubstrate material 3140, as shown by step 3190. The substrate material3140 is diced or cut resulting in a single cell 1110 on the sheet asdiced. The single cell 1110 is adhesively bonded to the second half 3130of the pacemaker 3100, as shown in step 3191. The electronics 3150 arethen placed onto the battery 1110 to form a circuit with the battery1110, as depicted by step 3192. The first half 3131 of the enclosure isplaced over the second half 3130 to form the assembled pacemaker 3100.

FIG. 32A is a perspective cutaway view of a watch 3200. The watchincludes a case 3210 and a band 3212 for strapping onto a person'swrist. Within the case 3210 is a solar cell 3220 and an LCD 3222. Thesolar cell 3220 is attached to the battery or series of battery cells1110. The LCD 3222 is attached to the battery and electronic (notshown). The battery powers the LCD 3222 and is associated to electronicsassociated with the watch 3200. The solar cell 3220 recharges thebattery 1110 more or less continuously. Both the solar cell 3220 and theLCD 3222 appear at the crystal or glass portion of the watch.Advantageously, this type of watch can be sealed forever so that it canbe made absolutely watertight.

Another embodiment of a watch is shown in FIG. 32B. In this particularinstance, a circular-shaped solar cell 3240 is positioned atop acircular-shaped battery cell 1110. The circular-shaped solar cellincludes an opening 3241 therein. A set of hands for an analog watch maybe inserted through the opening. The crystal or glass face of the watchwill then be opened to the solar cell 3240 so that it can continuouslycharge the battery 1110, which in turn powers the working portion of thewatch.

Described above are an improved method and system for fabrication ofsolid-state energy devices and the solid-state energy devices per se. Insome embodiments, the present method focuses the energy for formingfilms having fewer defects and/or certain crystal properties directly ata certain film. By focusing the energy, collateral damage to other partsof a structure or device are minimized. Accordingly, a wider array ofmaterials, devices and structures are available with which an energystorage device or energy conversion device is fabricated according tothe present invention.

In one embodiment, the method includes depositing a first film on asubstrate by depositing a first material to a location on the substrate,and supplying energized ions of a second material different than thefirst material to the location on the substrate to control growth of acrystalline structure of the first material at the location. Electrolyteand anode layers are subsequently formed. In some embodiments, the filmis “annealed” as it is deposited. In some embodiments, the energy“annealing” the film is only directed at the material of the film.

In one embodiment, the secondary source is an ion source with thecapability of supplying energetic ions having an energy greater than 5eV. In another embodiment, the energy range is about 5 eV to about 3,000eV. In one embodiment, the energy range of is about 5 eV to about 1,000eV. The energy range in a further embodiment is about 10 eV to about 500eV. In another embodiment, the energy range is in the range of about 60eV to 150 eV. In some embodiments, the energy is in the range of about100 eV to about 200 eV. In some embodiments, the energy is in the rangeof about 50 eV to about 250 eV. In some embodiments, the energy is inthe range of about40 eV to about 275 eV. In some embodiments, the energyis in the range of about 30 eV to about 300 eV. In some embodiments, theenergy is in the range of about 20 eV to about 350 eV. In someembodiments, the energy is in the range of about 15 eV to about 400 eV.In another embodiment, the energy range is about 140 eV.

In some embodiments, the cathode layer is formed without apost-deposition anneal step being performed thereon as the presentmethod provides the necessary energy to grow a sufficiently crystallinelayer by use of the secondary source. In some embodiments, the cathodelayer is not annealed at all.

In some embodiments, the substrate is formed of a material that willdegrade due to thermal effects at a high temperature such as an annealtemperature for conventional cathode thin films. In one embodiment, thesubstrate will thermally degrade at a temperature of less than 700degrees Celsius. In one embodiment, the substrate will thermally degradeat a temperature of less than 300 degrees Celsius. In one embodiment,the substrate will thermally degrade at a temperature of less than 250degrees Celsius. In one embodiment, the substrate will thermally degradeat a temperature of less than 100 degrees Celsius. In some embodiments,the thermal degradation temperature is about600 degrees Celsius. In someembodiments, the thermal degradation temperature is about 550 degreesCelsius. In some embodiments, the thermal degradation temperature isabout 500 degrees Celsius. In some embodiments, the thermal degradationtemperature is about 450 degrees Celsius. In some embodiments, thethermal degradation temperature is about 400 degrees Celsius. In someembodiments, the thermal degradation temperature is about 350 degreesCelsius. In some embodiments, the thermal degradation temperature isabout 300 degrees Celsius. In some embodiments, the thermal degradationtemperature is about 250 degrees Celsius.

Some embodiments of the method include depositing a seed material on afirst film to assist in the low energy deposition of the lithiumintercalation material of a subsequent film thereon. In an embodiment,the seed material assists in orienting the crystal structure of thesubsequent film. In some embodiments, the seed layer is an electricallyconductive layer. In some embodiments, the seed material providesnucleation sites for the film deposited thereon. In some embodiments,the seed layer includes islands of material. In some embodiments, theseed layer includes at least one of Ta, TaN, Cr, and CrN. In someembodiments, the seed layer includes one or more of W, WN, Ru, and RuN.In some embodiments, the seed layer has a surface free energy that ishigher than a surface free energy of film material being grown thereon.

Another aspect of the present invention provides structure and methodsfor controlling the temperature of the substrate and any films formedthereon during subsequent depositing steps. This allows a moretemperature sensitive material to be used as the substrate whilepreventing thermal degradation effects of the substrate.

In one embodiment of the method, subsequent films, including theelectrolyte film and the anode film, are deposited using a depositionsource and another source. In one embodiment, the second source providesenergy to orient the crystalline structure of the electrolyte film andthe anode film and influence the stoichiometry of the resulting films.In some embodiments, these films are treated by energy from the secondsource treats the material from the deposition source as it directsmaterial to the target substrate.

In another embodiment of the method, the battery, and/or layers of thebattery are subject to a post fabrication cryogenic anneal to correctdefects in the crystalline structure. In some embodiments, the cryogenicanneal is repeated multiple times. In some embodiments, the cryogenicanneal cools the battery to about negative (−)160 degrees Celsius toabout negative (−)50 degrees Celsius. In some embodiments, the cryogenicanneal cools the battery to about negative (−)120 degrees Celsius toabout negative (−)50 degrees Celsius. In some embodiments, the cryogenicanneal cools the battery to about negative (−)100 degrees Celsius toabout negative (−)50 degrees Celsius. In some embodiments, the cryogenicanneal cools the battery to about negative (−)80 degrees Celsius toabout negative (−)50 degrees Celsius. In some embodiments, the cryogenicanneal cools the battery to about negative (−)150 degrees Celsius. Insome embodiments, the cryogenic anneal cools the battery to aboutnegative (−)110 degrees Celsius. In some embodiments, the cryogenicanneal cools the battery to about negative (−)90 degrees Celsius. Insome embodiments, the cryogenic anneal cools the battery to aboutnegative (−)75 degrees Celsius. In some embodiments, the cryogenicanneal cools the battery to about negative (−)25 degrees Celsius.

Another important aspect of the methods described herein pertains to thequality of the crystalline materials, e.g., size, of the crystallites inthe thin layer. Crystallite size relates to the electrical performanceof lithium intercalation materials in lithium batteries and in otherdevices. Crystallite size in the layers deposited according to themethods described herein is adequately large to achieve commerciallyviable electrical properties in the devices described herein. In someembodiments, the crystallite size is greater than about 200 Angstroms.In some embodiments, the crystallite size is greater than about 300Angstroms. In some embodiments, the crystallite size is greater thanabout 400 Angstroms. In some embodiments, the crystallite size isgreater than about 500 Angstroms. In some embodiments, the crystallitesize is greater than about 600 Angstroms. In some embodiments, thecrystallite size is greater than about 650 Angstroms.

The energy-storage devices, such as thin-film batteries, capacitors, andsupercapacitors include an ultra-thinned electrolyte film interposedbetween two electrode films. Such ultra-thinned electrolyte filmsimprove electrical performance of the energy-storage devices bydecreasing the resistance within the electrolyte layer while stillmaintaining the required electron insulating property between the twoelectrodes. In some embodiments, the electrolyte film allows ionictransport therethrough. In some embodiments, the film between theelectrodes is a dielectric material. By using the methods describedherein, such ultra-thin electrolyte films of high structural quality andstoichiometric control are fabricated.

It is to be understood that the above description is intended to beillustrative, and not restrictive. Although numerous characteristics andadvantages of various embodiments as described herein have been setforth in the foregoing description, together with details of thestructure and function of various embodiments, many other embodimentsand changes to details will be apparent to those of skill in the artupon reviewing the above description. The scope of the invention should,therefore, be determined with reference to the appended claims, alongwith the full scope of equivalents to which such claims are entitled.

1. A thin-film, rechargeable battery device, comprising: a substrate; aseed layer of a first material adjacent to the substrate; a first filmof a second material formed on the seed layer, wherein the secondmaterial is different from the first material, and wherein the seedlayer assists formation of desired crystal structures; an electrolytesecond film adjacent to the first film; and a third film adjacent to theelectrolyte second film.
 2. The device of claim 1, wherein the firstfilm and the third film include an intercalation material.
 3. The deviceof claim 1, wherein the first film includes an intercalation material.4. The device of claim 1, wherein the third film includes anintercalation material.
 5. The device of claim 1, wherein the deviceincludes a lithium battery.
 6. The device of claim 1, wherein the deviceincludes a thin-film lithium battery.
 7. The device of claim 1, whereinthe substrate has a thermal degradation temperature of less than about700 degrees Celsius.
 8. The device of claim 1, wherein the substrate hasa thermal degradation temperature of less than about 250 degreesCelsius.
 9. The device of claim 3, wherein the seed layer has a surfacefree energy that is higher than a surface free energy of theintercalation material of the first film.
 10. The device of claim 3,wherein the seed layer is amorphous to diminish undesirable growthstructures of the intercalation material of the first film.
 11. Thedevice of claim 3, wherein the seed layer is a fine-grainedpolycrystalline seed material to diminish undesirable growth structuresof the intercalation material of the first film.
 12. The device of claim1, wherein the seed layer is an electrically conductive seed material.13. The device of claim 1, wherein the substrate includes a contactlayer, and the seed layer is on the contact layer.
 14. The device ofclaim 1, wherein the seed layer includes chromium.
 15. The device ofclaim 1, wherein the seed layer includes chromium nitride.
 16. Thedevice of claim 1, wherein the seed layer includes tantalum.
 17. Thedevice of claim 1, wherein the seed layer includes tantalum nitride. 18.The device of claim 1, wherein the seed layer includes tungsten.
 19. Thedevice of claim 1, wherein the seed layer includes tungsten nitride. 20.The device of claim 1, wherein the seed layer includes ruthenium. 21.The device of claim 1, wherein the seed layer includes rutheniumnitride.
 22. A thin-film, rechargeable battery device, comprising: asubstrate; a seed layer of a first material adjacent to the substrate; afirst film of a second material formed on the seed layer, wherein thesecond material is different from the first material, and wherein theseed layer assists formation of desired crystal structures; anelectrolyte second film adjacent to the first film; and a third filmadjacent to the electrolyte second film, wherein both the first film andthe second film are formed of lithium intercalation material such thatthe energy-storage device includes a lithium ion rechargeable battery.23. A thin-film, rechargeable battery device, comprising: a substrate;means for seeding growth of a crystalline structure adjacent to thesubstrate; a first film formed on the means for seeding growth of thecrystalline structure, wherein the first film has the crystallinestructure and is of a material different from the means for seedinggrowth of the crystalline structure; an electrolyte second film adjacentto the first film; and a third film adjacent to the electrolyte secondfilm.
 24. The device of claim 23, wherein both the first film and thethird film include an intercalation material.
 25. The device of claim23, wherein only the first film includes an intercalation material. 26.The device of claim 23, wherein only the third film includes anintercalation material.
 27. The device of claim 23, wherein the deviceis a thin-film lithium battery.
 28. The device of claim 23, wherein themeans for seeding growth includes an electrically conductive seedmaterial.